US5543056A - Method of drinking water treatment with natural cationic polymers - Google Patents

Method of drinking water treatment with natural cationic polymers Download PDF

Info

Publication number
US5543056A
US5543056A US08/268,266 US26826694A US5543056A US 5543056 A US5543056 A US 5543056A US 26826694 A US26826694 A US 26826694A US 5543056 A US5543056 A US 5543056A
Authority
US
United States
Prior art keywords
chitosan
water
bentonite
coagulant
drinking water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
US08/268,266
Inventor
Susan E. Murcott
Donald R. F. Harleman
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Massachusetts Institute of Technology
Original Assignee
Massachusetts Institute of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Massachusetts Institute of Technology filed Critical Massachusetts Institute of Technology
Priority to US08/268,266 priority Critical patent/US5543056A/en
Assigned to MASSACHUSETTS INSTITUTE OF TECHNOLOGY reassignment MASSACHUSETTS INSTITUTE OF TECHNOLOGY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HARLEMAN, DONALD R.F., MURCOTT, SUSAN E.
Application granted granted Critical
Publication of US5543056A publication Critical patent/US5543056A/en
Assigned to U.S. DEPARTMENT OF COMMERCE reassignment U.S. DEPARTMENT OF COMMERCE CONFIRMATORY LICENSE (SEE DOCUMENT FOR DETAILS). Assignors: MASSACHUSSETS INSTITUTE OF TECHNOLOGY
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56Macromolecular compounds
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S210/00Liquid purification or separation
    • Y10S210/902Materials removed
    • Y10S210/917Color
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S210/00Liquid purification or separation
    • Y10S210/931Zebra mussel mitigation or treatment

Definitions

  • Chemical coagulants used in water treatment include inorganic coagulants and organic polymers.
  • Inorganic coagulants include conventional metal salts (e.g. aluminum sulfate Al 2 (SO 4 ) 3 ; ferric chloride (FeCl 3 ); lime (CaCO 3 ) and polymerized metal salts (e.g. polyaluminum chloride p-AlCl 3 ) or polyaluminum silicate sulfate (p-AlSiS).
  • the present invention is a method for treating drinking water using natural polymers that provide an alternate and improved means to achieve enhanced coagulation.
  • a preferred embodiment is a method of treating drinking water by adding a primary coagulant and coagulant aid to drinking water to form a mixture, the primary coagulant added in an amount effective to form a floc in the drinking water.
  • the primary coagulant comprises a natural, cationic polymer and the coagulant aid comprises an effective amount of a clay mineral.
  • the floc containing particles that cause turbidity and color is then separated from the drinking water.
  • the step of separating comprises separating suspended matter from drinking water by a method selected from the group consisting of gravity settling, filtration and flotation.
  • the natural, cationic polymer is chitosan or a cationic starch.
  • the coagulant aid is a clay mineral, most preferably bentonite. The primary coagulant and coagulant aid may be added simultaneously or sequentially. After addition, the mixture is agitated with the drinking water.
  • a preferred concentration weight ratio of natural polymer to clay mineral is between 1:5 and 1:20.
  • Another embodiment is a composition for removing turbidity, particles, and color from drinking water, that includes a natural, cationic polymer coagulant and clay mineral in a total amount effective to form a floc in the drinking water.
  • a natural, cationic polymer coagulant and clay mineral in a total amount effective to form a floc in the drinking water.
  • This includes a weight ratio coagulant/clay mineral of between about 1:5 to about 1:20.
  • the polymer coagulant includes chitosan or cationic starch.
  • the clay mineral is preferably bentonite.
  • the methods and compositions of the invention offer advantages when used for drinking water treatment processes.
  • FIG. 1 is a graph comparing percentage removal of turbidity from water taken from Fresh Pond in Cambridge, Mass. using various concentrations of alum (open circles) and chitosan/bentonite (closed circles).
  • FIG. 2 is a graph comparing percentage removal of color from Fresh Pond water using various concentrations of alum (open circles) and chitosan/bentonite (closed circles)
  • FIG. 3 is a graph comparing hydrogen ion concentration (pH units) in Fresh Pond water after treatment with various concentrations of with alum (open circles) and chitosan/bentonite (closed circles).
  • FIG. 4 is a graph comparing percentage removal of alkalinity from Fresh Pond water using various concentrations of alum (open circles) and chitosan/bentonite (closed circles).
  • FIG. 5 are representative results showing the effect of various concentrations of primary coagulants (chitosan/bentonite- closed circle; ferric chloride- open square; and alum- open circle) on percentage removal of turbidity from water taken from Wachusett Reservoir in Clinton, Mass.
  • primary coagulants chitosan/bentonite- closed circle; ferric chloride- open square; and alum- open circle
  • FIG. 6 are representative results showing the effect of various concentrations of primary coagulants (chitosan/bentonite--closed circle; alum--open circle) on percentage removal of color from Wachusett Reservoir water.
  • primary coagulants chitosan/bentonite--closed circle; alum--open circle
  • FIG. 7 is a graph showing the effect of various amounts of alum and chitosan/bentonite on hydrogen ion concentration (pH units) of Wachusett Reservoir water.
  • FIG. 8 is a graph comparing percentage removal of alkalinity from Wachusett Reservoir water using various concentrations of alum (open circles) and chitosan/bentonite (closed circles).
  • the invention pertains to combined use of certain natural organic cationic polymers as primary coagulants in combination with clay minerals as coagulant aids to remove particles, color, and turbidity from drinking water.
  • Applicants have made the discovery that the addition of certain natural, organic cationic polymers as primary coagulants in combination with clay minerals as coagulant aids will remove these contaminants from drinking water as well or better than either component alone or than many of the optimal chemical coagulant regimes (typically aluminum sulfate with or without a synthetic polymer) currently in use at most water treatment plants world-wide.
  • Turbidity in drinking water is caused primarily by inorganic and organic suspended particles whereas the color of drinking water is a qualitative indication of the presence of organic material.
  • Turbidity is a measure of the light-scattering properties of the particulate matter present. Because the light-scattering properties of different kinds of particles vary, turbidity does not give a direct measure of the number of particles present.
  • particle counters are now being applied to determine by direct measurement the actual number of particles removed by a given treatment. The methods described herein not only remove particles, as detected by either turbidity or particle count, but can be used to remove from drinking water pathogenic microorganisms such as Giardia cysts and Cryptosporidium associated with particles.
  • the objective of drinking water treatment is to produce a water that is biologically and chemically safe for human consumption and which is aesthetically pleasing in terms of odor, appearance and taste.
  • the principal contaminants which may be found in water include: particulate matter; color; hardness; iron and manganese, toxic organics, and water borne pathogens.
  • a combination of chemical and physical processes are typically used to purify potable water, typically consisting of coagulation/flocculation followed by settling, filtration and/or flotation.
  • Aluminum sulfate (Al 2 (SO 4 ) 3 *18H 2 O is by far the most frequently used coagulant in drinking water treatment.
  • New "Surface Water Treatment Rules" under the Safe Drinking Water Act will require "enhanced coagulation", i.e., the use of increased dosages of coagulant chemicals. This process is being prescribed in order to increase the removal of organic matter, which in turn will minimize the likelihood of the formation of disinfectant/disinfection by-products.
  • higher doses of the conventional metal salts will depress pH, reduce alkalinity and generate large quantities of sludge. Because both polynuclear salts and organic coagulants do not have these negative impacts, they are gaining new prominence.
  • coagulation is, in fact, distinct from flocculation and is defined as the process that causes the neutralization of charges or a reduction of the repulsion forces between particles.
  • the overall electrical charge associated with particles and organic matter in water is usually negative. Consequently, positively charged coagulants are added to neutralize the electrical charge.
  • Flocculation is defined as the aggregation of particles into larger agglomerations called "flocs.”
  • the coagulation step is virtually instantaneous, while the flocculation (transport) step requires some time for the flocs to develop.
  • flocs are developed by bubbling air into the water sample after coagulation to increase buoyancy of the coagulated material and bring the floc to the surface of the sample.
  • Effective coagulation/flocculation can remove particles over a wide range of particle sizes. Particles as small as 1 micron in size can be removed. Filtration improves particle removal over coagulation/flocculation only in the size range from 0.5 to 1.0 micron. Effective coagulation/flocculation can remove most suspended particles, colloidal color, bacteria (0.1-0.2 microns), Giardia cysts (5-15 microns), Cyptosporidium (4-7 microns), and most algae.
  • the term "effective dose” refers to a dose that is sufficient to produce the desired effect of removing particles, color, and the like.
  • primary coagulant refers to the first coagulant (typically a metal salt) added alone or in a sequence.
  • coagulant aid refers to a chemical (typically a cationic, synthetic organic polymer) which, when added with a primary coagulant, enhances the adherence of the particles.
  • An anionic or nonionic polymer generally of a high molecular weight, added after flocculation is initiated, will act as a "flocculant aid" by contributing to the aggregation of the floc.
  • water refers to municipal potable or drinking water systems and not municipal sewage or industrial wastewaters.
  • natural organic polymer means a naturally occurring (as opposed to man-made) organic, low to medium molecular weight, long-chained molecule of repeating linked units.
  • Natural organic polymers are preferred to metal salts because: 1. They are effective in very low dosages as compared to metal salts; 2. Low dosages of polymers reduce the volume of sludge produced (because the volume of sludge is partly a function of chemical dose); 3. Their effectiveness is less pH dependent than for metal salts; 4. Polymers improve the sludge dewatering process as compared to alum or iron salts and provide a high sludge density; 5. Polymers are generally more biodegradable than alum or iron salt sludges and therefore ease sludge digestion by microorganisms; 6. They are non-corrosive and easy to handle; 7. Polymers do not pose problems in terms of residual metals contamination. 8. They have only a slight impact on pH and alkalinity.
  • Natural organic polymers are preferably cationic such as cationic starches, for example, potato starch.
  • Exemplary cationic starches may be substituted to a degree of substitution that will vary upon the circumstances.
  • a relatively high degree of substitution (D.S) includes values greater than about 0.03.
  • Suitable substituents include tertiary and quaternary amine groups.
  • Cationic starches are obtainable from other sources, for example, waxy maize starch, corn starch, wheat starch, and rice starch. See, for example U.S. Pat. No. 5,071,512--(Bixler and Peats), incorporated herein by reference.
  • the most preferred cationic natural organic polymer is chitosan because it is an abundant and renewable resource, is biodegradable, and has been shown to stimulate plant growth (Brzeski, M. 1987, Chitin and Chitosan--Putting Waste to Good Use. INFOFISH International). Chitosan is non-petroleum-based and is non-toxic.
  • Chitosan is a modified form of chitin, the second most abundant natural polymer after cellulose.
  • chitosan is a positively-charged polysaccharide, composed of poly-N-acetyl-glucoamine units, linked by beta 1-4 bonds into a linear polymer. It is a linear polyamine whose amino groups are readily available for chemical reaction and salt formation with acids. It has a high charge density of one charge per glucosamine unit. The positive charge of chitosan interacts strongly with the negative charges typical in most natural waters.
  • the most available source of chitin is the shells of crustaceans.
  • Natural chitin is bound by protein and calcium carbonate which can be removed by various techniques. See, for example, the work by Peniston and Johnson in U.S. Pat. Nos. 3,533,940, 3,862,122 and 3,922,260, and 4,195,175, incorporated herein by reference. Typically, extraction begins with removal of proteins, followed by removal of mineral components with dilute hydrochloric acid. Removal of acetyl groups at an elevated temperature (about 130-150 degrees C.) readily forms chitosan. Chitosan (molecular weight about 10 6 ) is virtually insoluble in water and solubility is pH-dependent. Typically, solutions of chitosan are prepared in acetic acid, although other organic acids such as formic, adipic, malic, propionic or succinic acids are suitable.
  • Exemplary coagulation aids are clay minerals, which may exhibit both a cation exchange capacity and an anion exchange capacity but with a net negative surface charge relative to the surrounding solution. Electrostatic forces or ion exchange are the primary mechanisms by which polymers become attached to clay particles, which is then followed by bridging between particles. See, for example, Wesner, and Gulp, Handbook of Public Water Systems, New York: Van Nostrand Reinhold Co. 1986., incorporated herein by reference.
  • Clays are hydrated aluminosilicates of calcium, sodium, magnesium and iron. and have not previously been used as coagulant aids in drinking water treatment.
  • the most preferred clay is bentonite, a fine-grained inorganic clay of the mineral montmorillonite that assists in increasing the rate and efficiency of natural polymer coagulation.
  • Three-layer clays like bentonite exhibit the highest cation exchange capacity relative to other clays.
  • the term "bentonite” includes forms such as commercial bentonites, Western bentonite, Wyoming bentonite, Fullers Earth).
  • Bentonite and bentonite-type clays have been further defined as anionic clays such as sepiolite, nontronite, hectorite, saponite, volkonskite, sauconite, beidellite, allevarlite, illite, halloysite, and attapulgite (U.S. Pat. Nos. 4,749,444 and 4,753,710, incorporated herein by reference).
  • Bentonites have a negative charge and can add weight to the flocs, joining them together to produce larger, tougher, and faster settling flocs.
  • Methods of the invention include adding the natural polymer as the primary coagulant and the clay as the coagulant aid, either simultaneously or sequentially, to a drinking water sample. It is most preferred that the mixture be agitated to enhance binding of pollutants to the natural cationic polymer and clay.
  • chitosan and the coagulant aid bentonite are able to perform as well, or better, than alum alone or alum with a synthetic polymer in the removal of particulate matter and color from drinking water.
  • the preferred chitosan dose is between 0.5 to 1.0 mg/l and the preferred bentonite dose is between 5 and 10 mg/l.
  • alum reduced pH by 1.0 to 1.4 units, but chitosan plus bentonite lowered pH only by 0.1 to 0.2 units.
  • This Example illustrates experiments using the method of the invention performed on two Massachusetts municipal drinking water facilities.
  • Fresh Pond the terminal drinking water supply reservoir of the Cambridge Water Department (CWD) in Cambridge, Mass. and Wachusett Reservoir, a principal municipal water supply reservoir in the Massachusetts Water Resources Authority (MWRA) system in Clinton, Mass. were selected for detailed testing comparisons of alum and chitosan not simply because they are convenient local drinking water sources, but because each system faces difficult water treatment challenges in the near future.
  • CWD Cambridge Water Department
  • MWRA Massachusetts Water Resources Authority
  • CWD uses aluminum sulfate as the primary coagulant in a multiple-stage, 14 million gallons per day (mgd) water treatment plant which is comprised of rapid mix, flocculation, clarification, and sand filtration units.
  • mgd gallons per day
  • the resulting alum-based sludge has been discharged into Fresh Pond, which is also the City of Cambridge's terminal supply reservoir. This is not a long-term solids disposal option because Fresh Pond is filling up with sludge.
  • the purpose of the jar tests described below was to determine the effectiveness of chitosan alone and in combination with coagulation aids as an alternate coagulant to alum or ferric chloride in terms of dose, mixing time and speed, order of chemical addition, and temperature.
  • Solution Makeup--A 1% chitosan solution was prepared by adding 2 grams (dry basis) of chitosan to 100 ml of water, then adding 100 ml of 2 % acetic acid solution and mixing until completely dissolved. Chitosan was obtained from Protan Inc. of Raymond, Wash.
  • AWWA Americal Water Works Association
  • AWWA: Denver, Colo. Six jars are filled with raw water and alum or another primary coagulant is added to each jar in a range of appropriate concentrations. The solution is mixed rapidly for 2 minutes at 150 rpm, then stirred slowly for 30 minutes at 25 rpm. After 30 minutes of settling, a sample from each jar and also a raw water sample is decanted for analysis.
  • Raw water was sampled at the headworks to the Cambridge Water Department Plan.
  • the sample was an 80:20 blend of Fresh Pond and Stony Brook Reservoir water, the blend typically used by the City of Cambridge. Fresh samples were collected in the morning of each test day in 5 gallon plastic buckets and transported to the laboratory.
  • Water was sampled in 5 gallon plastic buckets from the aqueduct beneath the Wachusett Administration Building (Power House). Tests were performed in a laboratory set up on site.
  • Chitosan alone performed poorly in terms of turbidity and color removal.
  • bentonite obtained from American Colloid Company, 1500 W. Shure Drive, Arlington Hts, Ill. 60004-7803 708:392-4600, tradename "Acco Floc 350"
  • chitosan showed markedly improved results.
  • the optimal concentration of chitosan was 0.5 mg/l for Fresh Pond water.
  • Bentonite was evaluated in a range between 0 to 20 mg/l in increments of 1 mg/l. Both turbidity and color were best removed with a bentonite concentration of 9 mg/l; a range between 6 and 9 mg/l would be effective. (See FIGS. 1-4). Bentonite alone did not act as a coagulant and turbidity and color increased when bentonite was tested by itself. Bentonite did not improve the performance of alum. That bentonite acts as a coagulant aid rather than as a coagulant is evidenced by the fact that turbidity and color increased in drinking water rather than decreased when bentonite was tested by itself.
  • FIGS. 1 and 2 compare alum to chitosan/bentonite based on their respective optimal mixing procedures. These figures illustrate the best results obtained on the same day on the same water sample with the mixing procedure selected to show the given chemical to its best advantage.
  • pH was depressed only slightly relative to the raw water sample when chitosan/bentonite was the coagulant mixture--by 0.1 to 0.2 (FIG. 3). pH reduction was significant with alum addition, decreasing by 1.0 unit relative to the raw water sample.
  • Alkalinity decreased by 15 % from 26 to 22 mg/l (as CaCO3) over the range of effective chitosan/bentonite concentrations. Alkalinity decreased by more than 50% from 26 to 12 mg/l (as CaCO 3 ) over the range of effective alum concentrations (FIG. 4).
  • ferric chloride FeCl 3
  • PASS polyaluminum silica sulfate
  • Chitosan was tested as a coagulant aid.
  • Alum was used as the primary coagulant at 20 mg/l and chitosan was added as a coagulant aid in concentrations ranging from 0.2 to 2 mg/l. These tests did not show any advantage to using chitosan as a coagulant aid in Fresh Pond water.
  • Optimal dose was determined on the basis of turbidity and color concentration and percentage removal.
  • chitosan in combination with the clay product bentonite, showed the best results.
  • Chitosan was tested in a concentration range from 0.2 to 3.0 mg/l.
  • the most effective chitosan concentration range was from 0.5 to 1.5 mg/l; the recommended chitosan concentration for Wachusett Reservoir is 1.0 mg/l.
  • Bentonite was tested in a concentration range from 2 to 40 mg/l.
  • the most effective bentonite concentration range was from 5 to 12 mg/l; the recommended bentonite concentration for Wachusett Reservoir is 8 mg/l. (See FIGS. 5-9).
  • the optimal dose of alum as a primary coagulant ranged from 5 mg/l to 20 mg/l.
  • Magnifloc #573C (American Cyanamid) is a cationic polyamine
  • Magnifloc #587C (American Cyanamid) is a cationic polyacrylamide.
  • the synthetic cationic polymers tested were inconsistent in enhancing turbidity removal and usually provided no improvement in color removal. Although these polymers may have been successfully used as filtration aids, they were generally ineffective in improving coagulation of Wachusett Reservoir water under winter conditions. Bentonite did not improve the performance of alum at any dose.
  • Optimal chemical type and concentration tests were performed on a weekly basis throughout the 3-month test period.
  • the average concentration of chitosan/bentonite was 0.9/8 mg/l, that of alum was 11 mg/l, and that of alum/synthetic polymer was 15/2 mg/l.
  • Chitosan/bentonite (49% turbidity removal) outperformed the other two coagulants and coagulant aids (21 percent and 25 percent, respectively).
  • about 1.0 mg/l chitosan and 8 mg/l bentonite gave significantly better turbidity removal compared to the metal regimes.
  • Overall, chitosan with bentonite gave the best coagulation performance.
  • FIGS. 5 and 6 are representative results showing the 3 primary coagulants tested versus % removal of turbidity and color, respectively.
  • the poor performance of FeCl 3 in FIG. 5 may be due to the winter water temperatures.
  • the primary coagulant tests presented in FIGS. 5 and 6 were all performed at the standard AWWA mixing procedure. Chitosan with bentonite performed better than the metal salts according to the mixing procedure developed for metal salts. Other tests indicated that the modified mixing procedure did not improve alum's performance. However, slight increases in rapid mixing time improved turbidity and color removal for the chitosan/bentonite combination (data not shown). Overall, the mixing time and speed tests showed that coagulation efficiency of chitosan with bentonite benefits from slight modifications of the standard mixing procedure.
  • FIG. 7 shows that treatment with alum with polymer significantly decreased pH by 1.4 units from 6.8 to 5.4 over the range of effective coagulation concentrations.
  • treatment with chitosan/bentonite decreased pH by only 0.1 units from 6.9 to 6.8 over the range of effective bentonite concentrations.
  • the raw water alkalinity concentration of 4.2 mg/l dropped 64 % to 1.5 mg/l.
  • Turbidity removal using alum was poor at low water temperatures of 3 degrees Centigrade, the typical water temperature throughout the winter testing season. In contrast, both alum and chitosan/bentonite successfully removed color from drinking water at these low water temperatures.
  • This Example illustrates experiments using the method of the invention at an Illinois water purification plant in 1994.
  • SWPP Chicago South Water Purification Plant
  • the SWPP is one of the world's largest drinking water treatment plants, with an average daily flow of 418 mgd and a maximum flow of 850 mgd. It is a conventional water treatment plant using horizontal shaft flocculators, conventional sedimentation and granular filtration. The filter waste washwater is settled and the decant is periodically recycled back to the raw water inflow. Sludge is discharged to the sewerage system.
  • the crib intake is located about two miles off shore and connected to the plant header by a pipeline.
  • the second intake is located directly on the lake shore and consists of a basin with gates allowing raw water intake.
  • the use of shore water is dependent on demand. Demand greater than the capacity of the crib pipeline (approximately 500 mgd) necessitates the use of shore water.
  • bench-scale studies were performed at the SWPP to evaluate the natural polymers chitosan and starch as primary coagulants, with bentonite as a coagulant aid.
  • Raw water Taps in the SWPP laboratory provide samples from many different points in the treatment system. Shore water contained sufficient turbidity (1.1-4.3 NTU) to be able to show effects of bench-scale coagulation and filtration.
  • Table 4 gives an overview of turbidity in the entire system and shows the variability in some of the measures. (It should be noted that SWPP measures turbidity at many other points in the system. The points presented in Table 4 were selected to give a representative snapshot of the system). Header water shows the greatest fluctuation in turbidities, due to periods throughout the day when settled filter waste washwater is recycled to the raw water header. Clear-well and outlet water is typically about 0.10 to 0.15 NTU.
  • the prescribed dose of coagulant is added to each jar while mixing at a speed of 110 rpm for 1 minute.
  • particle count provides a direct measure of the number of particles.
  • a Met One (Grants Pass, Oreg.) particle counter at the SWPP was used. The reader is directed to "Operational Control of Coagulation and Filtration Processes" (AWWA, 1992, incorporated herein by reference) for a detailed description of this technique.
  • Use of a Met One Model 250 particle counter began at SWPP in October 1993 to improve process control. A 250 ml sample is placed in a beaker inside the instrument, and 25 ml samples are consecutively withdrawn. Data is reported in terms of numbers of particles. Each count is an average of three 25 ml runs. Particles are counted into six preset size ranges: 2-5, 5-10, 10-15, 15-20, 20-50 and >50 micron size ranges.
  • Alum is the primary coagulant in a dose range from 3 to 6 mg/l and the widely used cationic polymer, Dadmac (made by American Cyanamid--trade name "Magnifloc") is employed both as a coagulant aid and as a filtration aid.
  • Dadmac made by American Cyanamid--trade name "Magnifloc"
  • SWPP particle count analysis is performed three times per week at eight points in the system. These are grab samples, drawn from the appropriate laboratory tap. The first drawn sample is typically taken from the crib water tap at 8:00 am, and subsequent samples are drawn based on the detention time at each point in the system.
  • the SWPP particle count results for one day, Jun. 3, 1994, are given in Table 7:
  • the #1 shore water sample is a "settled water” sample, meaning it was allowed to settle for 20 minutes prior to analysis.
  • the total particle count of 6,562 for this shore sample indicates fewer particles than the full-plant shore sample count (7,205) shown in Table 7.
  • the filtered water shore sample has a particle count of 221. This is a surprisingly low count. Low turbidity readings, however, were also evidenced on filtered shore water samples.
  • a chitosan/bentonite chemical coagulant regime gave the best filtered water particle count results, followed by a starch/bentonite and a chitosan/Dadmac chemical regime.
  • Alum/Dadmac gave the least successful filtered water particle count results.
  • Alum alone, alum/Dadmac and chitosan/bentonite gave essentially the same filtered water turbidity, based on averages from multiple trials.
  • chitosan can be used as a primary coagulant, with bentonite as a coagulant aid, instead of using alum with chitosan as a coagulant aid.
  • a cationic potato starch used as a primary coagulant with bentonite gave good filtered water results, both for turbidity and particle count.
  • pH was reduced from 8.34 to 7.48 in the concentration range from 1 mg/l to 4 mg/l for alum; pH was reduced by 0.04 to 0.07 when chitosan/potato starch was used as the primary coagulant at effective concentrations.
  • Use of these natural polymer primary coagulants allows usee of lower concentrations of pH adjustment chemicals.
  • A alum dose (mg/l)
  • M miscellaneous chemical additions such as polymers, pH neutralizing chemical, bentonite etc. (mg/l)
  • the insoluble aluminum hydroxide complex Al(H 2 O) 3 (OH) 3 is thought to predominate in most water treatment plant sludges when alum is used. This species results in the production of 0.44 kg of chemical sludge for each kg of alum added. Any suspended solids present in the water will produce an equal amount of sludge. Polymers and clays will produce about one kg of sludge per kg of chemical addition See, Davis, M., and Cornwell, D., "Introduction to Environmental Engineering", 2nd Edition. McGraw-Hill, Inc., New York., 1985. Turbidity, especially in low turbidity waters, makes an insignificant contribution to sludge quantity.
  • Cost of alum $0.10/lb ($0.22/kg)
  • Cost of chitosan $3.00/lb ($6.60/kg)
  • Tables 11 and 12 Based on the sludge production estimate of 11,500 lb/day, column 3 of Tables 11 and 12 give the dollar cost per dry ton of sludge. These Tables illustrate the wide range of sludge handling and disposal costs. The better the sludge for land application (less metals, lower toxic organic levels), the greater the likelihood that the lower land application costs of Table 12 could pertain. Chitosan plus bentonite offers a more desirable sludge for land application.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)

Abstract

A method for treating water using natural polymers that provide an alternate and improved means to achieve enhanced coagulation is described. A method for removing particles, color, and color from drinking water, comprising adding a primary coagulant such as a natural, cationic polymer like chitosan or a cationic starch and a coagulant aid such as bentonite to drinking water to form a mixture. A preferred concentration weight ratio of natural polymer to clay mineral is between 1:5 and 1:20.
A composition for removing particles and color from drinking water is described that includes a natural, cationic polymer coagulant and clay mineral in a total amount effective to coagulate suspended material in the drinking water. The composition includes a weight ratio natural polymer coagulant/clay mineral of between about 1:5 to about 1:20.

Description

The work described herein was funded, in part, by MIT Sea Grant Number NA 90AA-D-SG424. The Government has certain rights in the invention.
BACKGROUND OF THE INVENTION
New rules proposed by the Environmental Protection Agency under the Safe Drinking Water Act are leading drinking water treatment professionals to re-evaluate present treatment capabilities and evaluate alternatives for the future. Depending on the size of the facility, water utilities using surface water as their source for drinking water will need to monitor a wider array of contaminants in the drinking water than heretofore. Monitoring results will lead to a determination as to whether enhanced surface water treatment is required to further protect end-users from microbial contaminants and disinfectant/disinfection by-products.
If higher-order drinking water treatment is needed, enhanced coagulation would be required. Chemical coagulants used in water treatment include inorganic coagulants and organic polymers. Inorganic coagulants include conventional metal salts (e.g. aluminum sulfate Al2 (SO4)3 ; ferric chloride (FeCl3); lime (CaCO3) and polymerized metal salts (e.g. polyaluminum chloride p-AlCl3) or polyaluminum silicate sulfate (p-AlSiS).
However, higher doses of chemical coagulants have drawbacks as well. The benefits and proven efficacy of aluminum sulfate, the most widely used coagulant in drinking water treatment, is offset by the problem of residual metal contamination contributed by the metal salt and by performance problems at low temperatures. Higher doses of metal salts will generate large quantities of sludge and will depress pH, thereby requiting additional doses of pH adjustment chemicals. Use of synthetic organic polymer coagulants such as polyacrylamides and polyamines are also problematic since they may be toxic under certain circumstances.
These concerns have led to a ban on the use of many synthetic polymers in drinking water treatment in Germany, (Jackson, 1992, P. 1992. New Draft European Standards for Drinking Water Treatment Chemicals, paper delivered at the Intertech Conference: Flocculants, Coagulants and Precipitants for Drinking and Wastewater Treatment. Oct. 29-30, 1992. Herndon, Va.), in the Netherlands (Jackson, 1992, id.), and in Japan (Aizawa, T. et. al. 1990, Problems with Introducing Synthetic Polyelectrolyte Coagulants into the Water Purification Process, Water Supply Vol 8. Jonkoping, pp 27-35.). Elsewhere, doses of synthetic polymer coagulants are regulated to control potential problems with impurities (National Sanitation Foundation, 1988. Drinking Water Treatment Chemicals--Health Effects. Ann Arbor, Mich. ANSI/NSF60).
Attempts have been made to employ natural polymeric materials as coagulants in removal of greases, fats, and oils from industrial wastewater. Laurent (U.S. Pat. No. 5,269,939) describes a method for recovering suspended fats, oils, greases, proteins, and minerals from animal and/or food processing industrial wastewater streams using chitosan and clay. The wastewater freed of these materials is intended for discharge to municipal sewage treatment plants and the recovered solid material is a potential animal feed or fuel source. His method is "applicable to waste streams having any combination of fats, oils, greases, minerals, and/or proteins." (U.S. Pat. No. 5,269,939). There is a need to employ natural polymer coagulants and coagulant aids in other treatment contexts (i.e. drinking water treatment) in order to remove different sets of contaminants (i.e. particles, measured as turbidity or as number of particles; color; disinfectant/disinfection by-products).
SUMMARY OF THE INVENTION
The present invention is a method for treating drinking water using natural polymers that provide an alternate and improved means to achieve enhanced coagulation.
A preferred embodiment is a method of treating drinking water by adding a primary coagulant and coagulant aid to drinking water to form a mixture, the primary coagulant added in an amount effective to form a floc in the drinking water. The primary coagulant comprises a natural, cationic polymer and the coagulant aid comprises an effective amount of a clay mineral. The floc containing particles that cause turbidity and color is then separated from the drinking water. In preferred methods, the step of separating comprises separating suspended matter from drinking water by a method selected from the group consisting of gravity settling, filtration and flotation.
Most preferably, the natural, cationic polymer is chitosan or a cationic starch. The coagulant aid is a clay mineral, most preferably bentonite. The primary coagulant and coagulant aid may be added simultaneously or sequentially. After addition, the mixture is agitated with the drinking water. A preferred concentration weight ratio of natural polymer to clay mineral is between 1:5 and 1:20.
Another embodiment is a composition for removing turbidity, particles, and color from drinking water, that includes a natural, cationic polymer coagulant and clay mineral in a total amount effective to form a floc in the drinking water. This includes a weight ratio coagulant/clay mineral of between about 1:5 to about 1:20. Preferably, the polymer coagulant includes chitosan or cationic starch. The clay mineral is preferably bentonite.
The methods and compositions of the invention offer advantages when used for drinking water treatment processes.
BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 is a graph comparing percentage removal of turbidity from water taken from Fresh Pond in Cambridge, Mass. using various concentrations of alum (open circles) and chitosan/bentonite (closed circles).
FIG. 2 is a graph comparing percentage removal of color from Fresh Pond water using various concentrations of alum (open circles) and chitosan/bentonite (closed circles)
FIG. 3 is a graph comparing hydrogen ion concentration (pH units) in Fresh Pond water after treatment with various concentrations of with alum (open circles) and chitosan/bentonite (closed circles).
FIG. 4 is a graph comparing percentage removal of alkalinity from Fresh Pond water using various concentrations of alum (open circles) and chitosan/bentonite (closed circles).
FIG. 5 are representative results showing the effect of various concentrations of primary coagulants (chitosan/bentonite- closed circle; ferric chloride- open square; and alum- open circle) on percentage removal of turbidity from water taken from Wachusett Reservoir in Clinton, Mass.
FIG. 6 are representative results showing the effect of various concentrations of primary coagulants (chitosan/bentonite--closed circle; alum--open circle) on percentage removal of color from Wachusett Reservoir water.
FIG. 7 is a graph showing the effect of various amounts of alum and chitosan/bentonite on hydrogen ion concentration (pH units) of Wachusett Reservoir water.
FIG. 8 is a graph comparing percentage removal of alkalinity from Wachusett Reservoir water using various concentrations of alum (open circles) and chitosan/bentonite (closed circles).
DETAILED DESCRIPTION OF THE INVENTION
The invention pertains to combined use of certain natural organic cationic polymers as primary coagulants in combination with clay minerals as coagulant aids to remove particles, color, and turbidity from drinking water. Applicants have made the discovery that the addition of certain natural, organic cationic polymers as primary coagulants in combination with clay minerals as coagulant aids will remove these contaminants from drinking water as well or better than either component alone or than many of the optimal chemical coagulant regimes (typically aluminum sulfate with or without a synthetic polymer) currently in use at most water treatment plants world-wide.
Turbidity in drinking water is caused primarily by inorganic and organic suspended particles whereas the color of drinking water is a qualitative indication of the presence of organic material. Turbidity is a measure of the light-scattering properties of the particulate matter present. Because the light-scattering properties of different kinds of particles vary, turbidity does not give a direct measure of the number of particles present. Although controlling turbidity is one of the most common process control methods in drinking water treatment, particle counters are now being applied to determine by direct measurement the actual number of particles removed by a given treatment. The methods described herein not only remove particles, as detected by either turbidity or particle count, but can be used to remove from drinking water pathogenic microorganisms such as Giardia cysts and Cryptosporidium associated with particles.
Drinking Water Treatment Methods
The objective of drinking water treatment is to produce a water that is biologically and chemically safe for human consumption and which is aesthetically pleasing in terms of odor, appearance and taste. The principal contaminants which may be found in water include: particulate matter; color; hardness; iron and manganese, toxic organics, and water borne pathogens. A combination of chemical and physical processes are typically used to purify potable water, typically consisting of coagulation/flocculation followed by settling, filtration and/or flotation.
Aluminum sulfate (Al2 (SO4)3 *18H2 O is by far the most frequently used coagulant in drinking water treatment. New "Surface Water Treatment Rules" under the Safe Drinking Water Act will require "enhanced coagulation", i.e., the use of increased dosages of coagulant chemicals. This process is being prescribed in order to increase the removal of organic matter, which in turn will minimize the likelihood of the formation of disinfectant/disinfection by-products. However, higher doses of the conventional metal salts will depress pH, reduce alkalinity and generate large quantities of sludge. Because both polynuclear salts and organic coagulants do not have these negative impacts, they are gaining new prominence.
This should be contrasted to municipal wastewater treatment methods, the primary objective of which is to produce an effluent that can be discharged without causing detrimental environmental impacts and industrial wastewater treatment methods, the primary objective of which is to produce a water which can be reused internally in a closed loop within the facility or a water which can be discharged either to a municipal wastewater treatment plant or to the environment. The major contaminants found in municipal wastewater include suspended solids (TSS), biochemical oxygen demand (BOD), the nutrients phosphorus and nitrogen, metals, and pathogens. The principal contaminants in industrial wastewater include TSS, BOD, heavy metals, toxic organics, fats, oils and grease. Physical, chemical and/or biological treatment unit processes may all be employed, depending on the contaminant(s) which must be removed.
Definitions
Chemical coagulation, the alteration of suspended and colloidal particles so they adhere to each other, is one type of chemical treatment process. Although the terms "cogulation" and "flocculation" are often used loosely and interchangeably, coagulation is, in fact, distinct from flocculation and is defined as the process that causes the neutralization of charges or a reduction of the repulsion forces between particles. The overall electrical charge associated with particles and organic matter in water is usually negative. Consequently, positively charged coagulants are added to neutralize the electrical charge. Flocculation is defined as the aggregation of particles into larger agglomerations called "flocs." The coagulation step is virtually instantaneous, while the flocculation (transport) step requires some time for the flocs to develop. Typically, flocs are developed by bubbling air into the water sample after coagulation to increase buoyancy of the coagulated material and bring the floc to the surface of the sample. Effective coagulation/flocculation can remove particles over a wide range of particle sizes. Particles as small as 1 micron in size can be removed. Filtration improves particle removal over coagulation/flocculation only in the size range from 0.5 to 1.0 micron. Effective coagulation/flocculation can remove most suspended particles, colloidal color, bacteria (0.1-0.2 microns), Giardia cysts (5-15 microns), Cyptosporidium (4-7 microns), and most algae.
The term "effective dose" refers to a dose that is sufficient to produce the desired effect of removing particles, color, and the like.
The term "primary coagulant" refers to the first coagulant (typically a metal salt) added alone or in a sequence.
The term "coagulant aid" refers to a chemical (typically a cationic, synthetic organic polymer) which, when added with a primary coagulant, enhances the adherence of the particles. An anionic or nonionic polymer, generally of a high molecular weight, added after flocculation is initiated, will act as a "flocculant aid" by contributing to the aggregation of the floc.
The term "water" refers to municipal potable or drinking water systems and not municipal sewage or industrial wastewaters.
The term "natural organic polymer" means a naturally occurring (as opposed to man-made) organic, low to medium molecular weight, long-chained molecule of repeating linked units.
Natural organic polymers are preferred to metal salts because: 1. They are effective in very low dosages as compared to metal salts; 2. Low dosages of polymers reduce the volume of sludge produced (because the volume of sludge is partly a function of chemical dose); 3. Their effectiveness is less pH dependent than for metal salts; 4. Polymers improve the sludge dewatering process as compared to alum or iron salts and provide a high sludge density; 5. Polymers are generally more biodegradable than alum or iron salt sludges and therefore ease sludge digestion by microorganisms; 6. They are non-corrosive and easy to handle; 7. Polymers do not pose problems in terms of residual metals contamination. 8. They have only a slight impact on pH and alkalinity.
Natural organic polymers are preferably cationic such as cationic starches, for example, potato starch. Exemplary cationic starches may be substituted to a degree of substitution that will vary upon the circumstances. A relatively high degree of substitution (D.S) includes values greater than about 0.03. Suitable substituents include tertiary and quaternary amine groups. Cationic starches are obtainable from other sources, for example, waxy maize starch, corn starch, wheat starch, and rice starch. See, for example U.S. Pat. No. 5,071,512--(Bixler and Peats), incorporated herein by reference.
The most preferred cationic natural organic polymer is chitosan because it is an abundant and renewable resource, is biodegradable, and has been shown to stimulate plant growth (Brzeski, M. 1987, Chitin and Chitosan--Putting Waste to Good Use. INFOFISH International). Chitosan is non-petroleum-based and is non-toxic.
Chitosan is a modified form of chitin, the second most abundant natural polymer after cellulose. Typically derived from the chitin found in the organic exoskeleta of crustacea such as crabs, shrimps, prawns and lobsters, but also available from fungi and elsewhere, chitosan is a positively-charged polysaccharide, composed of poly-N-acetyl-glucoamine units, linked by beta 1-4 bonds into a linear polymer. It is a linear polyamine whose amino groups are readily available for chemical reaction and salt formation with acids. It has a high charge density of one charge per glucosamine unit. The positive charge of chitosan interacts strongly with the negative charges typical in most natural waters. The most available source of chitin is the shells of crustaceans.
Natural chitin is bound by protein and calcium carbonate which can be removed by various techniques. See, for example, the work by Peniston and Johnson in U.S. Pat. Nos. 3,533,940, 3,862,122 and 3,922,260, and 4,195,175, incorporated herein by reference. Typically, extraction begins with removal of proteins, followed by removal of mineral components with dilute hydrochloric acid. Removal of acetyl groups at an elevated temperature (about 130-150 degrees C.) readily forms chitosan. Chitosan (molecular weight about 106) is virtually insoluble in water and solubility is pH-dependent. Typically, solutions of chitosan are prepared in acetic acid, although other organic acids such as formic, adipic, malic, propionic or succinic acids are suitable.
Exemplary coagulation aids are clay minerals, which may exhibit both a cation exchange capacity and an anion exchange capacity but with a net negative surface charge relative to the surrounding solution. Electrostatic forces or ion exchange are the primary mechanisms by which polymers become attached to clay particles, which is then followed by bridging between particles. See, for example, Wesner, and Gulp, Handbook of Public Water Systems, New York: Van Nostrand Reinhold Co. 1986., incorporated herein by reference.
Clays are hydrated aluminosilicates of calcium, sodium, magnesium and iron. and have not previously been used as coagulant aids in drinking water treatment. The most preferred clay is bentonite, a fine-grained inorganic clay of the mineral montmorillonite that assists in increasing the rate and efficiency of natural polymer coagulation. Three-layer clays like bentonite exhibit the highest cation exchange capacity relative to other clays. The term "bentonite" includes forms such as commercial bentonites, Western bentonite, Wyoming bentonite, Fullers Earth). Bentonite and bentonite-type clays have been further defined as anionic clays such as sepiolite, nontronite, hectorite, saponite, volkonskite, sauconite, beidellite, allevarlite, illite, halloysite, and attapulgite (U.S. Pat. Nos. 4,749,444 and 4,753,710, incorporated herein by reference). Bentonites have a negative charge and can add weight to the flocs, joining them together to produce larger, tougher, and faster settling flocs.
Methods of the invention include adding the natural polymer as the primary coagulant and the clay as the coagulant aid, either simultaneously or sequentially, to a drinking water sample. It is most preferred that the mixture be agitated to enhance binding of pollutants to the natural cationic polymer and clay.
Knowledge of the appropriate mixture of natural cationic polymer and clay for one type of drinking water system cannot be used to predict the appropriate mixture for another drinking water system. The principal factors affecting coagulation include the type of coagulant, dosage of coagulant, mixing time and speed, order of coagulant addition, pH and alkalinity, temperature, properties of the natural organic matter in the raw drinking water (e.g. hydrophilic vs. hydrophobic, specific UV absorbance), and the like. Thus, the exact proportions of the ingredients used in the present methods must be determined de novo for each water treatment site. Generally, we have found that a weight ratio of coagulant to coagulant aid works best with a ratio of 1:5 to about 1:20. A general means for determining the appropriate proportions entail the use of the standard jar test procedure as described in Hudson, H. E. Jr. Water Clarification Processes/Practical Design and Evaluation. New York: Van Nostrand Reinhold Co. 1982, incorporated herein by reference.
The methods discussed herein have been shown to markedly enhance the removal of particles, organic matter that forms color, and turbidity from drinking water. Significantly, low doses of the natural polymer chitosan and the coagulant aid bentonite are able to perform as well, or better, than alum alone or alum with a synthetic polymer in the removal of particulate matter and color from drinking water. The preferred chitosan dose is between 0.5 to 1.0 mg/l and the preferred bentonite dose is between 5 and 10 mg/l. In the range of effective doses, alum reduced pH by 1.0 to 1.4 units, but chitosan plus bentonite lowered pH only by 0.1 to 0.2 units. Water treated with chitosan/bentonite will require less subsequent chemical treatment to neutralize the water. Alkalinity testing indicated that, in the range of optimal doses, alkalinity is reduced by 12% to 15% with chitosan plus bentonite and by over 50% to 64 % with alum.
The invention will now be illustrated by the following, non-limiting examples.
EXAMPLE 1 Treatment with Chitosan/Bentonite
This Example illustrates experiments using the method of the invention performed on two Massachusetts municipal drinking water facilities.
A. Description of the Water Systems--Fresh Pond and Wachusett Reservoir
Fresh Pond, the terminal drinking water supply reservoir of the Cambridge Water Department (CWD) in Cambridge, Mass. and Wachusett Reservoir, a principal municipal water supply reservoir in the Massachusetts Water Resources Authority (MWRA) system in Clinton, Mass. were selected for detailed testing comparisons of alum and chitosan not simply because they are convenient local drinking water sources, but because each system faces difficult water treatment challenges in the near future.
CWD--Fresh Pond
CWD uses aluminum sulfate as the primary coagulant in a multiple-stage, 14 million gallons per day (mgd) water treatment plant which is comprised of rapid mix, flocculation, clarification, and sand filtration units. For three decades, the resulting alum-based sludge has been discharged into Fresh Pond, which is also the City of Cambridge's terminal supply reservoir. This is not a long-term solids disposal option because Fresh Pond is filling up with sludge.
MWRA--Wachusett Reservoir
Wachusett Reservoir, built in 1898, is the water supply system which provides the greater Boston area with over 300 million gallons of water per day.
B. Raw Water Characteristics
During the winter/spring test period, the average raw water characteristics of Fresh Pond and Wachusett Reservoir were as shown in Table 1:
              TABLE 1                                                     
______________________________________                                    
AVERAGE RAW WATER CHARACTERISTICS                                         
                        Wachusett                                         
                Fresh Pond                                                
                        Reservoir                                         
______________________________________                                    
Turbidity (NTU)     1.5      0.53                                         
Apparent Color (CU)                                                       
                  22        14                                            
pH                  7.4     6.8                                           
Alkalinity (as CaCO3)                                                     
                  26        4.2                                           
Temperature (degrees C.)                                                  
                   8*       3                                             
______________________________________                                    
 *Temperature at time of sampling. Fresh pond samples were not tested on  
 site.                                                                    
 Average temperature at time of jar tests was 18 degrees C.               
Additional information on Wachusett Reservoir raw water characteristics is found in Table 2 and is taken from Edzward, J., Renckhow, D., and Paralkar, A. 1991. Analysis and Characterization of Organic Matter in the Water Supplies. Technical Memorandum. MWRA Pilot Treatment Program/Safe Drinking Water Act Compliance Plan, Subtask 1.2.2, Boston, Mass. October, 1991.
              TABLE 2                                                     
______________________________________                                    
ADDITIONAL DATA ON WACHUSETT RESERVOIR                                    
RAW WATER                                                                 
                      Wachusett                                           
                      Reservoir                                           
______________________________________                                    
Total Organic Carbon (TOC) (mg/l)                                         
                        3.1                                               
Dissolved Organic Carbon (DOC) (mg/l)                                     
                        3.0                                               
UV Absorbance (254 nm) (cm.sup.-1)                                        
                        .70                                               
Trihalomethane Formation Potential                                        
                        155                                               
(THMFP) (ug/l)                                                            
______________________________________                                    
In common with other chemical coagulants, the performance of chitosan can be evaluated through jar tests, an important tool for determining the efficacy of coagulation.
The purpose of the jar tests described below was to determine the effectiveness of chitosan alone and in combination with coagulation aids as an alternate coagulant to alum or ferric chloride in terms of dose, mixing time and speed, order of chemical addition, and temperature.
A standard Phipps & Bird jar test apparatus with six rectangular 2-liter jars was used. Turbidity was analyzed using a HACH Model 2100P portable turbidimeter according to EPA Method 180.1 (nephelometric). Apparent color was analyzed using a Hach Model DR/2000 spectrophotometer on unfiltered samples, according to the Platinum-Cobalt method (HACH Method 8025). This procedure assigns the wavelength of 455 nm as the dominant wavelength. pH was analyzed using a Hach One pH Meter. Alkalinity (as CaCO3) was determined using a HACH Digital Titrator.
Twenty-five jar test series were conducted during November and December, 1992, on water sampled from the headworks to the Cambridge Water Department Treatment Plant. At Wachusett Reservoir, over thirty jar test series were conducted during the months of February, March, and April, 1993, on water sampled from the aqueduct beneath the Wachusett Administration Building (Power House).
C. Procedure
1. Solution Makeup--A 1% chitosan solution was prepared by adding 2 grams (dry basis) of chitosan to 100 ml of water, then adding 100 ml of 2 % acetic acid solution and mixing until completely dissolved. Chitosan was obtained from Protan Inc. of Raymond, Wash.
2. Mixing Regime--Two basic mixing regimes were established:
AWWA Standard Mixing Procedure
The standard Americal Water Works Association (AWWA) jar test procedure is as follows (AWWA, 1978, Simplified Procedures for Water Examination. AWWA Manual M12. AWWA: Denver, Colo.): Six jars are filled with raw water and alum or another primary coagulant is added to each jar in a range of appropriate concentrations. The solution is mixed rapidly for 2 minutes at 150 rpm, then stirred slowly for 30 minutes at 25 rpm. After 30 minutes of settling, a sample from each jar and also a raw water sample is decanted for analysis.
Modified Mixing Procedure
According to some studies, energy input during the rapid mixing stage should be higher with organic polymers when tested as primary coagulants than with metal salts (Fettig, J. et. al., Synthetic Organic Polymers as Primary Coagulants in Wastewater Treatment, Water Supply, Vol. 8. Jonkoping, 1990). The modified mixing procedure is as follows: Each of the 6 jars are filled with raw water. Bentonite and chitosan are added simultaneously or sequentially and mixed at 150 rpm for 4 minutes. Mixing speed is reduced to 50 rpm for 30 minutes. The mixer is turned off and flocs are allowed to settle for 30 minutes. Experiments were also conducted at various other mixing times and speeds in order to determine the optimal conditions.
3. Sampling
Raw water was sampled at the headworks to the Cambridge Water Department Plan. The sample was an 80:20 blend of Fresh Pond and Stony Brook Reservoir water, the blend typically used by the City of Cambridge. Fresh samples were collected in the morning of each test day in 5 gallon plastic buckets and transported to the laboratory. At Wachusett Reservoir, water was sampled in 5 gallon plastic buckets from the aqueduct beneath the Wachusett Administration Building (Power House). Tests were performed in a laboratory set up on site.
D. Results--Cambridge Water Department, Fresh Pond Chitosan/Bentonite Optimal Dose
Chitosan alone performed poorly in terms of turbidity and color removal. However, in combination with bentonite (obtained from American Colloid Company, 1500 W. Shure Drive, Arlington Hts, Ill. 60004-7803 708:392-4600, tradename "Acco Floc 350"), chitosan showed markedly improved results.
The initial experiments tested chitosan in a range between 0 and 2.0 mg/l in increments of 0.1 mg/l. The optimal concentration of chitosan was 0.5 mg/l for Fresh Pond water. Bentonite was evaluated in a range between 0 to 20 mg/l in increments of 1 mg/l. Both turbidity and color were best removed with a bentonite concentration of 9 mg/l; a range between 6 and 9 mg/l would be effective. (See FIGS. 1-4). Bentonite alone did not act as a coagulant and turbidity and color increased when bentonite was tested by itself. Bentonite did not improve the performance of alum. That bentonite acts as a coagulant aid rather than as a coagulant is evidenced by the fact that turbidity and color increased in drinking water rather than decreased when bentonite was tested by itself.
Comparison of Alum versus Chitosan/Bentonite
Alum was found to perform best when tested with the AWWA standard mixing procedure. Chitosan/bentonite was found to perform best when tested with the modified mixing procedure. FIGS. 1 and 2 compare alum to chitosan/bentonite based on their respective optimal mixing procedures. These figures illustrate the best results obtained on the same day on the same water sample with the mixing procedure selected to show the given chemical to its best advantage.
With 0.5 mg/l chitosan plus 9 mg/l bentonite, turbidity % removal was slightly improved (FIG. 1) and color % removal (FIG. 2) was significantly improved compared to using 20 to 25 mg/l alum.
pH was depressed only slightly relative to the raw water sample when chitosan/bentonite was the coagulant mixture--by 0.1 to 0.2 (FIG. 3). pH reduction was significant with alum addition, decreasing by 1.0 unit relative to the raw water sample.
Alkalinity decreased by 15 % from 26 to 22 mg/l (as CaCO3) over the range of effective chitosan/bentonite concentrations. Alkalinity decreased by more than 50% from 26 to 12 mg/l (as CaCO3) over the range of effective alum concentrations (FIG. 4).
Other Metal Salts and Polymers Tested
Two other metal salts, ferric chloride (FeCl3) and polyaluminum silica sulfate (PASS), a polymerized metal salt, were evaluated. Both chemicals performed comparably to alum at similar concentrations.
Chitosan as a Coagulant Aid
Chitosan was tested as a coagulant aid. Alum was used as the primary coagulant at 20 mg/l and chitosan was added as a coagulant aid in concentrations ranging from 0.2 to 2 mg/l. These tests did not show any advantage to using chitosan as a coagulant aid in Fresh Pond water.
E. Results--Wachusett Reservoir Water Chitosan/Bentonite Optimal Dose
Optimal dose was determined on the basis of turbidity and color concentration and percentage removal. In terms of these parameters, chitosan, in combination with the clay product bentonite, showed the best results. Chitosan was tested in a concentration range from 0.2 to 3.0 mg/l. The most effective chitosan concentration range was from 0.5 to 1.5 mg/l; the recommended chitosan concentration for Wachusett Reservoir is 1.0 mg/l. Bentonite was tested in a concentration range from 2 to 40 mg/l. The most effective bentonite concentration range was from 5 to 12 mg/l; the recommended bentonite concentration for Wachusett Reservoir is 8 mg/l. (See FIGS. 5-9).
Alum with and without Synthetic Polymer--Optimal Dose
The optimal dose of alum as a primary coagulant ranged from 5 mg/l to 20 mg/l. Several synthetic cationic organic polymers, Magnifloc #573C and #587C, were tested as coagulant aids in conjunction with alum. Magnifloc #573C (American Cyanamid) is a cationic polyamine and Magnifloc #587C (American Cyanamid) is a cationic polyacrylamide.
At an optimal polymer dose of 2 mg/l, the synthetic cationic polymers tested were inconsistent in enhancing turbidity removal and usually provided no improvement in color removal. Although these polymers may have been successfully used as filtration aids, they were generally ineffective in improving coagulation of Wachusett Reservoir water under winter conditions. Bentonite did not improve the performance of alum at any dose.
Comparison of Alum versus Chitosan/Bentonite
Optimal chemical type and concentration tests were performed on a weekly basis throughout the 3-month test period. For the turbidity removal tests, the average concentration of chitosan/bentonite was 0.9/8 mg/l, that of alum was 11 mg/l, and that of alum/synthetic polymer was 15/2 mg/l. Chitosan/bentonite (49% turbidity removal) outperformed the other two coagulants and coagulant aids (21 percent and 25 percent, respectively). Thus, about 1.0 mg/l chitosan and 8 mg/l bentonite gave significantly better turbidity removal compared to the metal regimes. Overall, chitosan with bentonite gave the best coagulation performance.
Other chemicals were tested and compared to chitosan/bentonite or alum. These chemicals included ferric chloride, a variety of chitosan products, a variety of clay products, and some synthetic organic polymer coagulants, including Dadmac, polyacrylamides, and polyamines.
FIGS. 5 and 6 are representative results showing the 3 primary coagulants tested versus % removal of turbidity and color, respectively. The poor performance of FeCl3 in FIG. 5 may be due to the winter water temperatures.
Effect of the Mixing Regime
The primary coagulant tests presented in FIGS. 5 and 6 were all performed at the standard AWWA mixing procedure. Chitosan with bentonite performed better than the metal salts according to the mixing procedure developed for metal salts. Other tests indicated that the modified mixing procedure did not improve alum's performance. However, slight increases in rapid mixing time improved turbidity and color removal for the chitosan/bentonite combination (data not shown). Overall, the mixing time and speed tests showed that coagulation efficiency of chitosan with bentonite benefits from slight modifications of the standard mixing procedure.
pH and Alkalinity
In contrast to metal salts, chitosan with bentonite does not decrease pH. FIG. 7 shows that treatment with alum with polymer significantly decreased pH by 1.4 units from 6.8 to 5.4 over the range of effective coagulation concentrations. In contrast, treatment with chitosan/bentonite decreased pH by only 0.1 units from 6.9 to 6.8 over the range of effective bentonite concentrations.
Alkalinity declined sharply with the increased addition of alum. At the effective alum dose of 10 mg/l, the raw water alkalinity concentration of 4.2 mg/l dropped 64 % to 1.5 mg/l. In contrast, alkalinity dropped by only 12% at the effective chitosan dose of 1.0 mg/l with 10 mg/l bentonite (See FIG. 8).
Temperature
Turbidity removal using alum was poor at low water temperatures of 3 degrees Centigrade, the typical water temperature throughout the winter testing season. In contrast, both alum and chitosan/bentonite successfully removed color from drinking water at these low water temperatures.
EXAMPLE 2 Treatment with Chitosan/Bentonite or Cationic Starch/Bentonite
This Example illustrates experiments using the method of the invention at an Illinois water purification plant in 1994.
A. Description of the Chicago South Water Purification Plant (SWPP)
The SWPP is one of the world's largest drinking water treatment plants, with an average daily flow of 418 mgd and a maximum flow of 850 mgd. It is a conventional water treatment plant using horizontal shaft flocculators, conventional sedimentation and granular filtration. The filter waste washwater is settled and the decant is periodically recycled back to the raw water inflow. Sludge is discharged to the sewerage system.
The City of Chicago pumps raw water from Lake Michigan using two intakes. The crib intake is located about two miles off shore and connected to the plant header by a pipeline. The second intake is located directly on the lake shore and consists of a basin with gates allowing raw water intake. The use of shore water is dependent on demand. Demand greater than the capacity of the crib pipeline (approximately 500 mgd) necessitates the use of shore water. During May and June, 1994, bench-scale studies were performed at the SWPP to evaluate the natural polymers chitosan and starch as primary coagulants, with bentonite as a coagulant aid.
Parameters Investigated
The parameters investigated included: temperature, pH, turbidity, and particle count. Turbidity was measured using a Hach 2100P portable turbidimeter. Particle count was measured using a Met One Model 250 A (Grants Pass, Oreg.) particle counter. The reader is directed to Operational Control of Coagulation and Filtration Processes (AWWA, 1992, incorporated herein by reference) for a detailed description of this technique.
Raw water: Taps in the SWPP laboratory provide samples from many different points in the treatment system. Shore water contained sufficient turbidity (1.1-4.3 NTU) to be able to show effects of bench-scale coagulation and filtration.
              TABLE 3                                                     
______________________________________                                    
Raw Water Turbidities                                                     
        Range Turbidity                                                   
                   Average Turbidity                                      
        NTU (MIT)  NTU (MIT)                                              
______________________________________                                    
Crib      0.6-1.2      0.9                                                
Shore     1.1-4.3      2.5                                                
Header    9.7-9.9      9.8                                                
______________________________________                                    
Turbidity throughout the system, according to several different measures, is given in Table 4:
              TABLE 4                                                     
______________________________________                                    
Turbidity at SWPP                                                         
        May 31-  May 31-                                                  
        June 4, '94                                                       
                 June 4, '94                                              
                            1993 Annual                                   
        (assayed by                                                       
                 (present   Average (assayed                              
        SWPP)    work)      by SWPP)                                      
______________________________________                                    
Crib      0.5        0.8        3.8                                       
Shore     1.1        2.5        7.1                                       
Header    1.3        9.8        4.6                                       
Settling Basin                                                            
          0.8        1.0                                                  
#3 Effluent                                                               
Clearwell #3                                                              
           0.11       0.15                                                
79th St. Outlet                                                           
           0.11                  0.14                                     
______________________________________                                    
Table 4 gives an overview of turbidity in the entire system and shows the variability in some of the measures. (It should be noted that SWPP measures turbidity at many other points in the system. The points presented in Table 4 were selected to give a representative snapshot of the system). Header water shows the greatest fluctuation in turbidities, due to periods throughout the day when settled filter waste washwater is recycled to the raw water header. Clear-well and outlet water is typically about 0.10 to 0.15 NTU.
Jar Tests
A standard Phipps & Bird jar test apparatus with six rectangular 2-liter jars was used throughout the Illinois study.
1. Two liters of raw water are added to each jar.
2. The prescribed dose of coagulant is added to each jar while mixing at a speed of 110 rpm for 1 minute.
3. If a coagulant aid is considered, it is added during the last 15 seconds of the rapid mix stage.
4. The water is flocculated according to the following scheme:
80 rpm for 7.5 minutes;
50 rpm for 7.5 minutes;
35 rpm for 5 minutes.
5. The water is allowed to settle for 20 minutes (0 rpm).
6. For settled water testing, 250 ml is decanted for turbidity analysis ("settled water turbidities"); 500 ml is decanted for particle count analysis.
7. For filtered water testing, 70 ml of the 250 ml sample of settled water is used for the turbidity filterability test. For particle count analysis, an additional 500 ml is decanted for the filterability test.
Filtration Tests
For turbidity analysis, 250 ml of settled water was decanted. Twenty ml of this sample was used to wash the filter, then 50 ml was vacuum filtered (with a Fisher pump and Millipore glassware) though 1.0 micron glass filters (Gelman Science Product #61631). Whatman #1 filters (11 micron nominal size) were also tested for comparative purposes. The 1 micron filters used in the MIT study gave conservative data in comparison with actual full-scale filter performance.
Particle Count
Many contaminants of concern to the water industry are either particles or associated with particles. While particle measurement has traditionally been taken by the indirect means of turbidity or suspended solids concentration, particle count provides a direct measure of the number of particles.
A Met One (Grants Pass, Oreg.) particle counter at the SWPP was used. The reader is directed to "Operational Control of Coagulation and Filtration Processes" (AWWA, 1992, incorporated herein by reference) for a detailed description of this technique. Use of a Met One Model 250 particle counter began at SWPP in October 1993 to improve process control. A 250 ml sample is placed in a beaker inside the instrument, and 25 ml samples are consecutively withdrawn. Data is reported in terms of numbers of particles. Each count is an average of three 25 ml runs. Particles are counted into six preset size ranges: 2-5, 5-10, 10-15, 15-20, 20-50 and >50 micron size ranges.
Chemicals Used at the SWPP
The City of Chicago uses prechlorination for zebra mussel control. Alum is the primary coagulant in a dose range from 3 to 6 mg/l and the widely used cationic polymer, Dadmac (made by American Cyanamid--trade name "Magnifloc") is employed both as a coagulant aid and as a filtration aid.
Chemicals Tested
The chemicals tested are listed in Table 5:
              TABLE 5                                                     
______________________________________                                    
May 31-June 4, 1994                                                       
PRODUCT  CHARACTERISTICS  FUNCTION                                        
______________________________________                                    
Alum     Aluminum sulfate primary coagulant                               
Dadmac   synthetic cationic polymer                                       
                          coagulant aid                                   
Chitosan natural cationic polymer                                         
                          primary coagulant and                           
                          coagulant aid                                   
Bentonite                                                                 
         montmorillonite clay with                                        
                          coagulant aid                                   
         negative surface charge                                          
Starch   natural cationic polymer                                         
                          primary coagulant                               
Alginate natural anionic polymer                                          
                          flocculant aid                                  
Carrageenan                                                               
         natural anionic polymer                                          
                          flocculant aid                                  
______________________________________                                    
RESULTS Primary Coagulant Evaluation
Turbidity
After initial work allowed the determination of the lowest optimal primary coagulant concentrations, multiple tests were run at that optimum. Three to five tests each were run with the following chemical regimes:
*3 mg/l alum
*3 mg/l alum+0.35 mg/l Dadmac
*0.5 mg/l chitosan+5 mg/l bentonite
Results of these tests are given in Table 6:
                                  TABLE 6                                 
__________________________________________________________________________
Average Results for Different Chemical Regimes                            
          Average                                                         
                 Average                                                  
                        Average Average                                   
          Settled                                                         
                 Settled                                                  
                        Filtered                                          
                                Filtered                                  
          Turbidity                                                       
                 Turbidity                                                
                        Turbidity Conc.                                   
                                Turbidity %                               
          Conc. (NTU)                                                     
                 % Removal                                                
                        (NTU)   Removal                                   
__________________________________________________________________________
3 mg/l alum                                                               
          0.8    64     0.65    70                                        
3 mg/l alum +                                                             
          1.4    46     0.66    78                                        
0.35 mg/l Dadmac                                                          
0.5 mg/l chitosan +                                                       
          1.9    20     0.66    74                                        
5 mg/l bentonite                                                          
__________________________________________________________________________
Although the alum regimes gave considerably better settled water results, all three regimes gave essentially comparable average filtered turbidity concentrations.
The experiments typically tested chitosan in dosages between 0.25 to 1.0 mg/l. The use of bentonite as a coagulant aid improved settleability.
Particle Count
At SWPP, particle count analysis is performed three times per week at eight points in the system. These are grab samples, drawn from the appropriate laboratory tap. The first drawn sample is typically taken from the crib water tap at 8:00 am, and subsequent samples are drawn based on the detention time at each point in the system. The SWPP particle count results for one day, Jun. 3, 1994, are given in Table 7:
                                  TABLE 7                                 
__________________________________________________________________________
Particle Count of SWPP Treatment System Samples                           
        PARTICLE SIZE (microns)                                           
        2-5  5-10 10-15                                                   
                      15-25                                               
                          25-50                                           
                              >50 TOTAL                                   
__________________________________________________________________________
Crib    2,332                                                             
             325  25  5   2   0   2,689                                   
Shore   5,464                                                             
             1,474                                                        
                  172 57  36  2   7,205                                   
Header  4,740                                                             
             1,220                                                        
                  235 69  30  1   6,295                                   
Settling Basin                                                            
        2,781                                                             
             583  75  15  1   0   3,455                                   
Effluent                                                                  
Clearwell #2                                                              
        16    5   1   1   0   0   23                                      
N. Reservoir                                                              
        21    4   1   1   0   0   27                                      
S. Reservoir                                                              
        62   11   2   1   0   0   76                                      
73rd St. Outlet                                                           
        18    5   1   1   0   0   25                                      
79th St. Outlet                                                           
        11    2   0   0   0   0   13                                      
Distribution                                                              
        195  31   4   1   0   0   231                                     
__________________________________________________________________________
Looking at the total particle count results in the last column of Table 7, we see that the number of particles in crib water is less than half that of shore or header water. Settling basin effluent water has a higher particle count than the crib water. This is probably on account of the various chemicals added. Particle count drops significantly after filtration, as evidenced in Clearwell #2, the North and South Reservoirs, and the two outlets. Particle count increases in the distribution system; particles are perhaps contributed by the distribution pipes themselves.
The ten individual bench-scale study samples analyzed by particle count on the same day, Jun. 3, 1994, are presented in Table 8. The best bench-scale test results are about equivalent to the number of particles in the distribution system at the full-scale:
______________________________________                                    
Particle Count of Bench-Scale Study Samples                               
June 3, 1994                                                              
               Settled Water     Filtered Water                           
               Total Particle    Total Particle                           
           #   Count      #      Count                                    
______________________________________                                    
Shore        1     6,562      2    221                                    
0.75 mg/l chitosan +                                                      
             3     7,191      4    257                                    
0.35 mg/l Dadmac                                                          
3 mg/l alum +                                                             
             5     1,304      6    823                                    
0.35 mg/l Dadmac                                                          
0.5 mg/l chitosan +                                                       
             7     7,195      8    163                                    
5 mg/l bentonite                                                          
5 mg/l starch +                                                           
             9     7,006      10   251                                    
5 mg/l bentonite                                                          
______________________________________                                    
In common with samples #3, #5, #7, and #9, the #1 shore water sample is a "settled water" sample, meaning it was allowed to settle for 20 minutes prior to analysis. The total particle count of 6,562 for this shore sample indicates fewer particles than the full-plant shore sample count (7,205) shown in Table 7. The filtered water shore sample has a particle count of 221. This is a surprisingly low count. Low turbidity readings, however, were also evidenced on filtered shore water samples. Of the four chemical coagulant regimes analyzed as filtered samples, chitosan/bentonite ranked #1 for the lowest filtered water particle count, starch/bentonite and chitosan/Dadmac ranked closely as #2 and #3, and alum/Dadmac trailed the other chemical regimes.
Other Natural Polymer Tests
Three cationic potato starches (designated A, P and N- obtained from AVEBE America, St. Louis, Mo., 217:423-2288) were tested as primary coagulants with bentonite as a coagulant aid. Although all the starches increased settled water turbidity above the raw shore water turbidity of 2.0 NTU, Starch N gave the best filtered water results, as shown in Table 9. This is the same starch on which the particle analysis was run (Table 7, samples #9 and #10):
              TABLE 9                                                     
______________________________________                                    
Potato Starch and Bentonite Tests                                         
(Raw Shore Water Turbidity = 2.0 NTU)                                     
                   Settled Filtered                                       
                   Turbidity                                              
                           Turbidity                                      
                   NTU     NTU                                            
______________________________________                                    
5 mg/l starch A + 5 mg/l bentonite                                        
                     2.7       0.76                                       
5 mg/l starch P + 5 mg/l bentonite                                        
                     2.7       0.81                                       
5 mg/l starch N + 5 mg/l bentonite                                        
                     2.2       0.63                                       
______________________________________                                    
pH
The use of alum in a dose range of 3-6 mg/l at SWPP depresses pH and requires the use of a roughly comparable dose of lime for pH adjustment. Effective doses of three natural cationic polymers: chitosan, and starch had only a very slight effect on pH.
Chitosan as a Coagulant Aid
Chitosan as a coagulant aid with 4 mg/l alum was compared to chitosan as a primary coagulant with bentonite. Results are given in Table 10:
              TABLE 10                                                    
______________________________________                                    
Chitosan as a Coagulant Aid                                               
                Raw Water Settled  Filtered                               
                Turbidity Turbidity                                       
                                   Turbidity                              
Chemical Regime NTU       NTU      NTU                                    
______________________________________                                    
4 mg/l alum + 0.5 mg/l                                                    
                1.1       0.65     0.61                                   
chitosan                                                                  
0.5 mg/l chitosan + 5 mg/l                                                
                1.1       1.58     0.63                                   
bentonite                                                                 
______________________________________                                    
The filtered water results in Table 10 suggest that chitosan can be just as effective at the low dose of 0.5 mg/l as a primary coagulant, provided it is used in conjunction with the coagulant aid bentonite.
CONCLUSIONS
1. A chitosan/bentonite chemical coagulant regime gave the best filtered water particle count results, followed by a starch/bentonite and a chitosan/Dadmac chemical regime. Alum/Dadmac gave the least successful filtered water particle count results.
2. Alum alone, alum/Dadmac and chitosan/bentonite gave essentially the same filtered water turbidity, based on averages from multiple trials.
3. At an effective dose of 0.5 mg/l, chitosan can be used as a primary coagulant, with bentonite as a coagulant aid, instead of using alum with chitosan as a coagulant aid.
4. A cationic potato starch used as a primary coagulant with bentonite gave good filtered water results, both for turbidity and particle count.
5. pH was reduced from 8.34 to 7.48 in the concentration range from 1 mg/l to 4 mg/l for alum; pH was reduced by 0.04 to 0.07 when chitosan/potato starch was used as the primary coagulant at effective concentrations. Use of these natural polymer primary coagulants allows usee of lower concentrations of pH adjustment chemicals.
Sludge Production
We will assume an alum/polymer recommendation of 10 mg/l and 1.5 mg/l polymer and a chitosan/bentonite recommendation of 1.0 mg/l chitosan and 8 mg/l bentonite for use in a water treatment plant.
A simple equation to evaluate sludge production is given as follows:
M.sub.s =86.4 Q(0.44A+SS+M)                                (Equation 1)
where
Ms =dry sludge produced (kg/day)
Q=plant flow (m3 /sec)=(13.1 m3 /sec assumed)
A=alum dose (mg/l)
SS=suspended solids in raw water (mg/l)
M=miscellaneous chemical additions such as polymers, pH neutralizing chemical, bentonite etc. (mg/l)
The insoluble aluminum hydroxide complex Al(H2 O)3 (OH)3 is thought to predominate in most water treatment plant sludges when alum is used. This species results in the production of 0.44 kg of chemical sludge for each kg of alum added. Any suspended solids present in the water will produce an equal amount of sludge. Polymers and clays will produce about one kg of sludge per kg of chemical addition See, Davis, M., and Cornwell, D., "Introduction to Environmental Engineering", 2nd Edition. McGraw-Hill, Inc., New York., 1985. Turbidity, especially in low turbidity waters, makes an insignificant contribution to sludge quantity.
Based on equation 1, 1.0 mg/l chitosan plus 8 mg/l bentonite will produce about the same amount of sludge as 15 mg/l alum plus 1.5 mg/l polymer.
Cost
A rough estimate can be made of the relative costs of using alum and a polymer versus using chitosan and bentonite at Wachusett Reservoir. The following assumptions pertain:
Flow=300 mgd (1.1×10.sup.9 l/day=13.1m.sup.3 /sec)
Alum concentration=10 mg/l
Polymer concentration=1.5 mg/l
Chitosan concentration=1.0 mg/l
Bentonite concentration=8 mg/l
Cost of alum=$0.10/lb ($0.22/kg)
Cost of polymer=$1.70/lb ($3.74/kg)
Cost of chitosan=$3.00/lb ($6.60/kg)
Cost of bentonite=$0.10/lb ($0.22/kg)
Alum+Polymer Cost
Alum
10 mg/L×$0.22/kg×10-6 kg/mg×1.1×109 l /day=$2,400/day
Polymer
1.5 mg/L×$3.74/kg×10-6 kg/mg×1.1×109 l/day=$6,200/day
Chitosan+Bentonite Cost
Chitosan
10 mg/L×$6.60/kg×10-6 kg/mg×1.1×109 l/day=$7,300/day
Bentonite
8 mg/L×$0.22/kg×10-6 kg/mg×1.1×109 l/day=$1,900/day
TOTAL=$9,200/day
In terms of the chemical cost alone, the chitosan/bentonite cost is only slightly more expensive than the alum/polymer cost, Besides the chemical cost, the chitosan plus bentonite chemical combination would have other operating cost implications. Because chitosan plus bentonite has only a slight impact on pH, cost savings would occur from reduced demand for neutralizing agents. A significant cost savings from the use of chitosan and bentonite would also be in sludge handling and disposal. The increased options for disposal of a beneficial sludge would outweigh the slight additional chemical cost. Column 2 of Tables 11 and 12 gives total present worth cost estimates for various sludge handling and disposal alternatives for one large drinking water system (e.g., MWRA).
Based on the sludge production estimate of 11,500 lb/day, column 3 of Tables 11 and 12 give the dollar cost per dry ton of sludge. These Tables illustrate the wide range of sludge handling and disposal costs. The better the sludge for land application (less metals, lower toxic organic levels), the greater the likelihood that the lower land application costs of Table 12 could pertain. Chitosan plus bentonite offers a more desirable sludge for land application.
              TABLE 11                                                    
______________________________________                                    
COST ESTIMATES OF SLUDGE PROCESSING                                       
AND LANDFILL                                                              
                 Total       Cost                                         
                 Present Worth                                            
                             ($/dry ton                                   
Option           ($ million) of sludge)                                   
______________________________________                                    
Freeze/Thaw Lagoons                                                       
                 17.0        405                                          
Plate and Frame  25.9        617                                          
Belt Press + F/T Lagoons                                                  
                 18.0        429                                          
Belt Press + Drying Lagoons                                               
                 19.2        457                                          
______________________________________                                    
              TABLE 12                                                    
______________________________________                                    
COST ESTIMATES OF SLUDGE PROCESSING &                                     
LAND APPLICATION                                                          
                 Total       Cost                                         
                 Present Worth                                            
                             ($/dry ton                                   
Option           ($ million) of sludge)                                   
______________________________________                                    
Freeze/Thaw Lagoons                                                       
                 13.3        317                                          
Plate and Frame  19.5        463                                          
Belt Press + F/T Lagoons                                                  
                 14.3        341                                          
Belt Press + Drying Lagoons                                               
                 12.7        302                                          
Belt Press       10.7        254                                          
______________________________________                                    
Equivalents
It should be understood that various changes and modifications of the preferred embodiments may be made within the scope of the invention. Thus it is intended that all matter contained in the above description be interpreted in an illustrative and not limited sense.

Claims (9)

We claim:
1. A method of treating drinking water containing suspended matter, comprising:
adding a primary coagulant and coagulant aid to drinking water to form a mixture, the primary coagulant added in an amount effective to form a floc including said suspended matter in the drinking water and comprising a natural, cationic polymer selected from the group consisting of chitosan and cationic starch, the coagulant aid comprising an effective amount of a clay mineral, wherein the weight ratio of coagulant:coagulant aid is between about 1:5 to about 1:20; and
separating the flocculated suspended matter from the drinking water.
2. The method of claim 1, wherein the step of separating comprises separating suspended matter from drinking water by a method selected from the group consisting of gravity settling, filtration and flotation.
3. The method of claim 1, wherein the suspended matter comprises particles and organic matter that cause the drinking water to have a color.
4. The method of claim 1, wherein the step of adding a natural, cationic polymer comprises adding chitosan.
5. The method of claim 1 or 4, wherein the step of adding a clay mineral comprises adding bentonite.
6. The method of claim 5, wherein the step of adding comprises adding the primary coagulant and coagulant aid simultaneously and agitating the drinking water.
7. The method of claim 5, wherein the step of adding a clay mineral comprises adding about 5 to about 10 mg/l bentonite.
8. The method of claim 4, wherein the step of adding a natural, cationic polymer comprises adding about 0.5 to about 1.0 mg/l chitosan.
9. The method of claim 1, wherein the step of adding a natural, cationic polymer comprises adding cationic starch.
US08/268,266 1994-06-29 1994-06-29 Method of drinking water treatment with natural cationic polymers Expired - Fee Related US5543056A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US08/268,266 US5543056A (en) 1994-06-29 1994-06-29 Method of drinking water treatment with natural cationic polymers

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US08/268,266 US5543056A (en) 1994-06-29 1994-06-29 Method of drinking water treatment with natural cationic polymers

Publications (1)

Publication Number Publication Date
US5543056A true US5543056A (en) 1996-08-06

Family

ID=23022192

Family Applications (1)

Application Number Title Priority Date Filing Date
US08/268,266 Expired - Fee Related US5543056A (en) 1994-06-29 1994-06-29 Method of drinking water treatment with natural cationic polymers

Country Status (1)

Country Link
US (1) US5543056A (en)

Cited By (70)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5900211A (en) * 1995-10-26 1999-05-04 Purepulse Technologies Deactivation of organisms using high-intensity pulsed polychromatic light
US5948279A (en) * 1997-09-25 1999-09-07 Ohio University Method and apparatus for controlling macrofoulers in on-demand water conduits
WO2000000436A1 (en) * 1998-06-30 2000-01-06 Aqua-Aerobic Systems, Inc. Treatment process for removing microbial contaminants suspended in wastewater
WO2000000437A1 (en) * 1998-06-30 2000-01-06 Aqua-Aerobic Systems, Inc. Potable water system and process
US6120690A (en) * 1997-09-16 2000-09-19 Haase; Richard Alan Clarification of water and wastewater
US6184302B1 (en) * 1997-05-12 2001-02-06 Clariant Corporation Substantially water-insoluble cationized solids, and their preparation and use
US6235339B1 (en) * 1999-03-04 2001-05-22 Purdue Research Foundation Method of treating a meat processing plant waste stream
US6241896B1 (en) * 1999-03-05 2001-06-05 Associated Water Industries, L.L.C. Auto dosage determination method and apparatus for coagulant control in the treatment of water
US6261460B1 (en) 1999-03-23 2001-07-17 James A. Benn Method for removing contaminants from water with the addition of oil droplets
US6264841B1 (en) 1995-06-30 2001-07-24 Helen E. A. Tudor Method for treating contaminated liquids
WO2003010233A1 (en) * 2001-07-26 2003-02-06 Ppg Industries Ohio, Inc. Compositions incorporating chitosan for paint detackification
US6537939B1 (en) 2000-10-20 2003-03-25 Anthony Reid Harvey Porous grog composition, water purification device containing the porous grog and method for making same
US6565803B1 (en) 1998-05-13 2003-05-20 Calgon Carbon Corporation Method for the inactivation of cryptosporidium parvum using ultraviolet light
KR100405268B1 (en) * 2001-06-19 2003-11-12 신성메디아 주식회사 The contactive filter for purification of the polluted water and waste water
US20030209499A1 (en) * 2000-09-29 2003-11-13 Haase Richard A. Clarification of water and wastewater
US6827874B2 (en) 2000-06-27 2004-12-07 The Procter & Gamble Co. Water treatment compositions
US20050124482A1 (en) * 2000-10-20 2005-06-09 Harvey Anthony R. Silver chloride treated water purification device containing the porous grog and method for making same
US20050242043A1 (en) * 2004-04-30 2005-11-03 Nichols Everett J Method for removing Cryptosporidium oocysts from water
EP1607406A1 (en) 2004-06-18 2005-12-21 Taiwan Hopax Chems. Mfg. Co., Ltd Chemically modified polyaminosaccharide by a hydrocarbyl sultone compound
US20060131242A1 (en) * 2004-12-21 2006-06-22 Brady Brent S Flocculating agent for clarifying the water of man-made static water bodies
WO2006088901A1 (en) * 2005-02-15 2006-08-24 Halosource, Inc. Method for the removal of submicron particulates from chlorinated water by sequentially adding a cationic polymer followed by adding an anionic polymer
US20060231499A1 (en) * 2005-04-18 2006-10-19 Ken Brummett Methods and compositions for wastewater treatment
CN1300011C (en) * 2005-06-06 2007-02-14 武汉理工大学 Environment protection type flocculation agent for treating water and its preparation process
CN1317203C (en) * 2005-06-06 2007-05-23 武汉理工大学 Composite flocculation agent of modified rectorite with polysaccharase
US20080035569A1 (en) * 2004-03-03 2008-02-14 Haim Wilder Water Treatment Device and Method Therefor
CN100389077C (en) * 2001-12-03 2008-05-21 中国人民解放军总后勤部军需装备研究所 Process and apparatus for purifying drinking water
WO2008060631A3 (en) * 2006-11-17 2008-07-10 Boc Group Inc Method of treating wastewater
KR100880603B1 (en) 2007-09-14 2009-01-30 주식회사 씨앤지 Method for coagulating sludge with use of chitosan and chitosan decomposition enzyme and manufacturing method for fertilizer
KR100880990B1 (en) 2007-09-14 2009-02-03 서정대 Method for coagulating sludge with use of chitosan and chitosan decomposition enzyme and manufacturing method for fertilizer
US20090206040A1 (en) * 2008-02-14 2009-08-20 Berg Michael C Systems and methods for removing finely dispersed particulate matter from a fluid stream
CN101885562A (en) * 2010-07-01 2010-11-17 杨国录 Remediation method of polluted water body of rivers and lakes
US20100294703A1 (en) * 2009-05-21 2010-11-25 Health And Beyond, Llc Water enhancement system
US20110000854A1 (en) * 2009-07-06 2011-01-06 Halosource, Inc. Use of a dual polymer system for enhanced water recovery and improved separation of suspended solids and other substances from an aqueous media
US20110006013A1 (en) * 2005-02-15 2011-01-13 Halosource, Inc. Method for the removal of submicron particulates from chlorinated water by sequentially adding a cationic polymer followed by adding an anionic polymer
US20110094970A1 (en) * 2009-10-27 2011-04-28 Kincaid Patrick D System, methods, processes and apparatus for removing finely dispersed particulate matter from a fluid stream
US20110131873A1 (en) * 2008-02-14 2011-06-09 David Soane Systems and methods for removing finely dispersed particulate matter from a fluid stream
US20110226706A1 (en) * 2010-03-22 2011-09-22 Water Security Corporation Filter comprising a halogen release system and chitosan
WO2011157902A1 (en) * 2010-06-17 2011-12-22 Neste Oil Oyj A method for harvesting algae
US20130015143A1 (en) * 2010-04-06 2013-01-17 Sijing Wang Non-destructive method for algae contaminated water treatment and algae harvest or removal
WO2013014373A1 (en) 2011-07-22 2013-01-31 Roquette Freres Potabilisation method
LT5926B (en) 2012-06-13 2013-04-25 Kauno technologijos universitetas Cationic starch flocculant and the method of production thereof
US8557123B2 (en) 2009-02-27 2013-10-15 Soane Energy, Llc Methods for removing finely dispersed particulate matter from a fluid stream
EP2723690A1 (en) * 2011-06-23 2014-04-30 Gavish-Galilee Bio Applications Ltd Method for pretreatment of wastewater and recreational water with nanocomposites
WO2014076435A1 (en) 2012-11-16 2014-05-22 Roquette Freres Potabilization process
US8821733B2 (en) 2009-09-29 2014-09-02 Soane Mining, Llc Systems and methods for recovering fine particles from fluid suspensions for combustion
US8980059B2 (en) 2009-08-12 2015-03-17 Nanopaper, Llc High strength paper
WO2014171812A3 (en) * 2013-04-18 2015-05-07 ZAINAL ABIDIN, Roslan Bin A composition for treating waste water
WO2015073919A1 (en) * 2013-11-14 2015-05-21 University Medical Pharmaceuticals Corporation Microneedles for therapeutic agent delivery with improved mechanical properties
US20150151221A1 (en) * 2007-06-13 2015-06-04 Haemonetics Corporation Method and device for the concentration of multiple microorganisms and toxins from large liquid toxins
WO2015118275A1 (en) * 2014-02-07 2015-08-13 Roquette Freres Process for thickening or dehydrating sludge
CN104876315A (en) * 2015-05-29 2015-09-02 鞍山中科美清节能环保技术有限公司 Water treatment flocculant
CN105084441A (en) * 2015-09-16 2015-11-25 太仓市国峰纺织印染有限责任公司 Printing and dyeing sewage treatment agent
US9233863B2 (en) 2011-04-13 2016-01-12 Molycorp Minerals, Llc Rare earth removal of hydrated and hydroxyl species
CN106348411A (en) * 2016-10-13 2017-01-25 王家财 Novel clean environment-friendly coagulant and production method thereof
US9587353B2 (en) 2012-06-15 2017-03-07 Nanopaper, Llc Additives for papermaking
CN107162143A (en) * 2017-07-01 2017-09-15 辽东学院 Dyeing waste water purifies flocculant and its dyeing waste water purification applications
WO2017158581A1 (en) * 2016-03-17 2017-09-21 Gavish-Galilee Bio Applications Ltd. Method for production of potable water
US9919938B2 (en) 2012-06-18 2018-03-20 Soane Mining, Llc Systems and methods for removing finely dispersed particles from mining wastewater
US9975787B2 (en) 2014-03-07 2018-05-22 Secure Natural Resources Llc Removal of arsenic from aqueous streams with cerium (IV) oxide compositions
CN108773890A (en) * 2018-06-12 2018-11-09 赵田田 A kind of purifying domestic sewage agent and the preparation method and application thereof
US10273169B2 (en) 2012-06-21 2019-04-30 Gavish-Galilee Bio Applications, Ltd. Method for pretreatment of wastewater with nanocomposites and bridging polymers
CN109761394A (en) * 2019-01-28 2019-05-17 合肥信拓高分子技术有限公司 A kind of stirring-type sewage-treatment plant
CN110217871A (en) * 2019-05-17 2019-09-10 茂名市水务投资集团有限公司 A kind of highly effective coagulation algae-removing method of the raw water containing algae
US11155479B2 (en) 2018-11-21 2021-10-26 Baker Hughes Holdings Llc Methods and compositions for removing contaminants from wastewater streams
WO2021257606A1 (en) * 2020-06-16 2021-12-23 Baker Hughes Oilfield Operations Llc Carbon disulfide-modified amine additives for separation of oil from water
US20220089463A1 (en) * 2020-09-22 2022-03-24 Aquom Sciences Llc Biopolymeric water treatment
CN114956292A (en) * 2022-05-13 2022-08-30 吉林农业大学 Method for pretreating soybean yellow serofluid by using chitosan flocculation
CN115092998A (en) * 2022-07-04 2022-09-23 庆阳新庄煤业有限公司新庄煤矿 Salt-reducing ash-reducing coal dust-removing flocculating agent for return air main roadway water collecting tank
US11572297B2 (en) * 2017-07-14 2023-02-07 Aquom Sciences Llc Biopolymeric water treatment
WO2024073798A1 (en) * 2022-10-03 2024-04-11 The University Of Sydney Composite coagulants

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3338828A (en) * 1964-07-29 1967-08-29 Joseph R Clark Purification of water supplies and aqueous wastes
US3533940A (en) * 1967-06-02 1970-10-13 Quintin P Peniston Method for treating an aqueous medium with chitosan and derivatives of chitin to remove an impurity
JPS4928115A (en) * 1972-07-14 1974-03-13
US3842005A (en) * 1970-07-01 1974-10-15 Staley Mfg Co A E Process of flocculating aqueous suspensions with cationic starch ethers
US3862122A (en) * 1972-02-16 1975-01-21 Quintin P Peniston Method of recovering chitosan and other by-products from shellfish waste and the like
US4018678A (en) * 1974-08-09 1977-04-19 Peniston Quintin P Method of and apparatus for fluid filtration and the like with the aid of chitosan
JPS52111893A (en) * 1976-03-17 1977-09-19 Taki Chem Co Ltd Water treating agent
US4053401A (en) * 1974-11-29 1977-10-11 Nichireki Chemical Inudstry Co., Ltd Sludge treating process
US4195175A (en) * 1978-01-03 1980-03-25 Johnson Edwin L Process for the manufacture of chitosan
US4765908A (en) * 1985-02-04 1988-08-23 Barbara Monick Process and composition for removing contaminants from wastewater
US5071512A (en) * 1988-06-24 1991-12-10 Delta Chemicals, Inc. Paper making using hectorite and cationic starch
US5178730A (en) * 1990-06-12 1993-01-12 Delta Chemicals Paper making
US5204452A (en) * 1990-11-14 1993-04-20 E. I. Du Pont De Nemours And Company N-halochitosans, their preparation and uses
US5269939A (en) * 1992-07-13 1993-12-14 Laurent Edward L Method of solids recovery for use in animal feed or as a fuel utilizing natural flocculents
US5393435A (en) * 1993-09-17 1995-02-28 Vanson L.P. Removal of organic contaminants from aqueous media

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3338828A (en) * 1964-07-29 1967-08-29 Joseph R Clark Purification of water supplies and aqueous wastes
US3533940A (en) * 1967-06-02 1970-10-13 Quintin P Peniston Method for treating an aqueous medium with chitosan and derivatives of chitin to remove an impurity
US3842005A (en) * 1970-07-01 1974-10-15 Staley Mfg Co A E Process of flocculating aqueous suspensions with cationic starch ethers
US3862122A (en) * 1972-02-16 1975-01-21 Quintin P Peniston Method of recovering chitosan and other by-products from shellfish waste and the like
JPS4928115A (en) * 1972-07-14 1974-03-13
US4018678A (en) * 1974-08-09 1977-04-19 Peniston Quintin P Method of and apparatus for fluid filtration and the like with the aid of chitosan
US4053401A (en) * 1974-11-29 1977-10-11 Nichireki Chemical Inudstry Co., Ltd Sludge treating process
JPS52111893A (en) * 1976-03-17 1977-09-19 Taki Chem Co Ltd Water treating agent
US4195175A (en) * 1978-01-03 1980-03-25 Johnson Edwin L Process for the manufacture of chitosan
US4765908A (en) * 1985-02-04 1988-08-23 Barbara Monick Process and composition for removing contaminants from wastewater
US5071512A (en) * 1988-06-24 1991-12-10 Delta Chemicals, Inc. Paper making using hectorite and cationic starch
US5178730A (en) * 1990-06-12 1993-01-12 Delta Chemicals Paper making
US5204452A (en) * 1990-11-14 1993-04-20 E. I. Du Pont De Nemours And Company N-halochitosans, their preparation and uses
US5269939A (en) * 1992-07-13 1993-12-14 Laurent Edward L Method of solids recovery for use in animal feed or as a fuel utilizing natural flocculents
US5393435A (en) * 1993-09-17 1995-02-28 Vanson L.P. Removal of organic contaminants from aqueous media

Non-Patent Citations (14)

* Cited by examiner, † Cited by third party
Title
"Jar Test of the Natural Polymer Chitosan", The American Water Works Association Water Quality Technology Conference Proceedings (presented Nov. 1993).
"MIT Jar Test of the Wachusett Reservoir Water Using the Natural Polymer Chitosan with Bentonite", Murcott (Jul. 1993).
"Shellfish May Help Treat Sewage", Civil Engineering News, vol. 4, No. 11, Dec. 1992.
"Some Shellfish With Your Sewage", Civil Engineering News.
Elizabeth A. Thomson, "Shellfish May Play Role in Sewage Treatment", MIT Tech Talk, Oct. 28, 1992.
Elizabeth A. Thomson, Shellfish May Play Role in Sewage Treatment , MIT Tech Talk, Oct. 28, 1992. *
Elizabeth Pennisi, "Chitin Craze", Science News, vol. 144, pp. 72-73, Jul. 13, 1993.
Elizabeth Pennisi, Chitin Craze , Science News, vol. 144, pp. 72 73, Jul. 13, 1993. *
Jar Test of the Natural Polymer Chitosan , The American Water Works Association Water Quality Technology Conference Proceedings (presented Nov. 1993). *
MIT Jar Test of the Wachusett Reservoir Water Using the Natural Polymer Chitosan with Bentonite , Murcott (Jul. 1993). *
Shellfish May Help Treat Sewage , Civil Engineering News, vol. 4, No. 11, Dec. 1992. *
Some Shellfish With Your Sewage , Civil Engineering News. *
Susumu Kawamura, "Effectiveness of Natural Polyelectrolytes in Water Treatment", Journal AWWA, pp. 88-91, Oct. 1991.
Susumu Kawamura, Effectiveness of Natural Polyelectrolytes in Water Treatment , Journal AWWA, pp. 88 91, Oct. 1991. *

Cited By (116)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6264841B1 (en) 1995-06-30 2001-07-24 Helen E. A. Tudor Method for treating contaminated liquids
US5900211A (en) * 1995-10-26 1999-05-04 Purepulse Technologies Deactivation of organisms using high-intensity pulsed polychromatic light
US6184302B1 (en) * 1997-05-12 2001-02-06 Clariant Corporation Substantially water-insoluble cationized solids, and their preparation and use
US6120690A (en) * 1997-09-16 2000-09-19 Haase; Richard Alan Clarification of water and wastewater
US5948279A (en) * 1997-09-25 1999-09-07 Ohio University Method and apparatus for controlling macrofoulers in on-demand water conduits
US6565803B1 (en) 1998-05-13 2003-05-20 Calgon Carbon Corporation Method for the inactivation of cryptosporidium parvum using ultraviolet light
WO2000000437A1 (en) * 1998-06-30 2000-01-06 Aqua-Aerobic Systems, Inc. Potable water system and process
US6110374A (en) * 1998-06-30 2000-08-29 Aqua-Aerobic Systems, Inc. Treatment process for removing microbial contaminants suspended in wastewater
WO2000000436A1 (en) * 1998-06-30 2000-01-06 Aqua-Aerobic Systems, Inc. Treatment process for removing microbial contaminants suspended in wastewater
US6235339B1 (en) * 1999-03-04 2001-05-22 Purdue Research Foundation Method of treating a meat processing plant waste stream
US6241896B1 (en) * 1999-03-05 2001-06-05 Associated Water Industries, L.L.C. Auto dosage determination method and apparatus for coagulant control in the treatment of water
US6261460B1 (en) 1999-03-23 2001-07-17 James A. Benn Method for removing contaminants from water with the addition of oil droplets
US6827874B2 (en) 2000-06-27 2004-12-07 The Procter & Gamble Co. Water treatment compositions
US20030209499A1 (en) * 2000-09-29 2003-11-13 Haase Richard A. Clarification of water and wastewater
US20050124482A1 (en) * 2000-10-20 2005-06-09 Harvey Anthony R. Silver chloride treated water purification device containing the porous grog and method for making same
US6537939B1 (en) 2000-10-20 2003-03-25 Anthony Reid Harvey Porous grog composition, water purification device containing the porous grog and method for making same
US7491330B2 (en) 2000-10-20 2009-02-17 Anthony Reid Harvey Silver chloride treated water purification device containing the porous grog and method for making same
KR100405268B1 (en) * 2001-06-19 2003-11-12 신성메디아 주식회사 The contactive filter for purification of the polluted water and waste water
US6673263B2 (en) * 2001-07-26 2004-01-06 Ppg Industries Ohio, Inc. Compositions incorporating chitosan for paint detackification
US20040084067A1 (en) * 2001-07-26 2004-05-06 Albu Michael L. Compositions incorporating chitosan for paint detackification
US6858093B2 (en) 2001-07-26 2005-02-22 Ppg Industries Ohio, Inc. Method for paint detackification using compositions containing chitosan
WO2003010233A1 (en) * 2001-07-26 2003-02-06 Ppg Industries Ohio, Inc. Compositions incorporating chitosan for paint detackification
CN100389077C (en) * 2001-12-03 2008-05-21 中国人民解放军总后勤部军需装备研究所 Process and apparatus for purifying drinking water
US20080035569A1 (en) * 2004-03-03 2008-02-14 Haim Wilder Water Treatment Device and Method Therefor
AU2005240579B2 (en) * 2004-04-30 2010-09-16 Nc Brands L.P. Method for removing cryptosporidium oocysts from water
WO2005108306A3 (en) * 2004-04-30 2006-11-09 Vanson Halosource Inc Method for removing cryptosporidium oocysts from water
US7157009B2 (en) * 2004-04-30 2007-01-02 Vanson Halosource, Inc. Method for removing Cryptosporidium oocysts from water
US20050242043A1 (en) * 2004-04-30 2005-11-03 Nichols Everett J Method for removing Cryptosporidium oocysts from water
US20060025583A1 (en) * 2004-06-18 2006-02-02 Taiwan Hopax Chemicals Manufacturing Company, Ltd. Chemically modified polyaminosaccharide by a hydrocarbyl sultone compound
US20050283004A1 (en) * 2004-06-18 2005-12-22 Hopax Chemicals Manufacturing Co., Ltd. Alkylsulfonated polyaminosaccharides
US8263763B2 (en) 2004-06-18 2012-09-11 Taiwan Hopax Chemicals Manufacturing Company, Ltd. Chemically modified polyaminosaccharide by a hydrocarbyl sultone compound
EP1607406A1 (en) 2004-06-18 2005-12-21 Taiwan Hopax Chems. Mfg. Co., Ltd Chemically modified polyaminosaccharide by a hydrocarbyl sultone compound
US7329356B2 (en) * 2004-12-21 2008-02-12 Aquagems Laboratories, Llc Flocculating agent for clarifying the water of man-made static water bodies
US20060131242A1 (en) * 2004-12-21 2006-06-22 Brady Brent S Flocculating agent for clarifying the water of man-made static water bodies
US20060196834A1 (en) * 2005-02-15 2006-09-07 Nichols Everett J Method for the removal of submicron particulates from chlorinated water by sequentially adding a cationic polymer followed by adding an anionic polymer
WO2006088901A1 (en) * 2005-02-15 2006-08-24 Halosource, Inc. Method for the removal of submicron particulates from chlorinated water by sequentially adding a cationic polymer followed by adding an anionic polymer
US20110006013A1 (en) * 2005-02-15 2011-01-13 Halosource, Inc. Method for the removal of submicron particulates from chlorinated water by sequentially adding a cationic polymer followed by adding an anionic polymer
US7790042B2 (en) 2005-02-15 2010-09-07 Halosource, Inc. Method for the removal of submicron particulates from chlorinated water by sequentially adding a cationic polymer followed by adding an anionic polymer
US20060231499A1 (en) * 2005-04-18 2006-10-19 Ken Brummett Methods and compositions for wastewater treatment
US7384573B2 (en) * 2005-04-18 2008-06-10 Ken Brummett Compositions for wastewater treatment
CN1300011C (en) * 2005-06-06 2007-02-14 武汉理工大学 Environment protection type flocculation agent for treating water and its preparation process
CN1317203C (en) * 2005-06-06 2007-05-23 武汉理工大学 Composite flocculation agent of modified rectorite with polysaccharase
WO2008060631A3 (en) * 2006-11-17 2008-07-10 Boc Group Inc Method of treating wastewater
US20150151221A1 (en) * 2007-06-13 2015-06-04 Haemonetics Corporation Method and device for the concentration of multiple microorganisms and toxins from large liquid toxins
US9522350B2 (en) * 2007-06-13 2016-12-20 Trustees Of Tufts College Method and device for the concentration of multiple microorganisms and toxins from large liquid toxins
KR100880990B1 (en) 2007-09-14 2009-02-03 서정대 Method for coagulating sludge with use of chitosan and chitosan decomposition enzyme and manufacturing method for fertilizer
KR100880603B1 (en) 2007-09-14 2009-01-30 주식회사 씨앤지 Method for coagulating sludge with use of chitosan and chitosan decomposition enzyme and manufacturing method for fertilizer
WO2009035279A1 (en) * 2007-09-14 2009-03-19 Clean & Green Co., Ltd Method for coagulating sludge with use of chitosan and chitosan decomposition enzyme and manufacturing method for fertilizer
EP2252404B1 (en) 2008-02-14 2018-12-05 Soane Mining LLC Systems and methods for removing finely dispersed particulate matter from a fluid stream
US20110131873A1 (en) * 2008-02-14 2011-06-09 David Soane Systems and methods for removing finely dispersed particulate matter from a fluid stream
US10562799B2 (en) 2008-02-14 2020-02-18 Soane Mining, Llc Systems and methods for removing finely dispersed particulate matter from a fluid stream
US10570037B2 (en) 2008-02-14 2020-02-25 Soane Mining, Llc Systems and methods for removing finely dispersed particulate matter from a fluid stream
US8349188B2 (en) * 2008-02-14 2013-01-08 Soane Mining, Llc Systems and methods for removing finely dispersed particulate matter from a fluid stream
US8353641B2 (en) * 2008-02-14 2013-01-15 Soane Energy, Llc Systems and methods for removing finely dispersed particulate matter from a fluid stream
US20090206040A1 (en) * 2008-02-14 2009-08-20 Berg Michael C Systems and methods for removing finely dispersed particulate matter from a fluid stream
US8557123B2 (en) 2009-02-27 2013-10-15 Soane Energy, Llc Methods for removing finely dispersed particulate matter from a fluid stream
US8696893B2 (en) 2009-05-21 2014-04-15 David Hall Water enhancement system
US20100294703A1 (en) * 2009-05-21 2010-11-25 Health And Beyond, Llc Water enhancement system
US8252172B2 (en) 2009-05-21 2012-08-28 David Hall Water enhancement system
US20110000854A1 (en) * 2009-07-06 2011-01-06 Halosource, Inc. Use of a dual polymer system for enhanced water recovery and improved separation of suspended solids and other substances from an aqueous media
US10040710B2 (en) 2009-07-06 2018-08-07 Dober Chemical Corporation Use of a dual polymer system for enhanced water recovery and improved separation of suspended solids and other substances from an aqueous media
US8980059B2 (en) 2009-08-12 2015-03-17 Nanopaper, Llc High strength paper
US8821733B2 (en) 2009-09-29 2014-09-02 Soane Mining, Llc Systems and methods for recovering fine particles from fluid suspensions for combustion
US20110094970A1 (en) * 2009-10-27 2011-04-28 Kincaid Patrick D System, methods, processes and apparatus for removing finely dispersed particulate matter from a fluid stream
US8945394B2 (en) 2009-10-27 2015-02-03 Soane Energy, Llc System, methods, processes and apparatus for removing finely dispersed particulate matter from a fluid stream
US20110226706A1 (en) * 2010-03-22 2011-09-22 Water Security Corporation Filter comprising a halogen release system and chitosan
US8980097B2 (en) 2010-03-22 2015-03-17 Water Security Corporation Filter comprising a halogen release system and chitosan
US20130015143A1 (en) * 2010-04-06 2013-01-17 Sijing Wang Non-destructive method for algae contaminated water treatment and algae harvest or removal
CN102892716A (en) * 2010-04-06 2013-01-23 通用电气公司 Non-destructive method for algae contaminated water treatment and algae harvest or removal
WO2011157902A1 (en) * 2010-06-17 2011-12-22 Neste Oil Oyj A method for harvesting algae
CN101885562A (en) * 2010-07-01 2010-11-17 杨国录 Remediation method of polluted water body of rivers and lakes
CN101885562B (en) * 2010-07-01 2011-10-26 杨国录 Remediation method of polluted water body of rivers and lakes
US9233863B2 (en) 2011-04-13 2016-01-12 Molycorp Minerals, Llc Rare earth removal of hydrated and hydroxyl species
EP2723690A1 (en) * 2011-06-23 2014-04-30 Gavish-Galilee Bio Applications Ltd Method for pretreatment of wastewater and recreational water with nanocomposites
EP2723690A4 (en) * 2011-06-23 2015-04-29 Gavish Galilee Bio Appl Ltd Method for pretreatment of wastewater and recreational water with nanocomposites
JP2014523342A (en) * 2011-07-22 2014-09-11 ロケット・フルーレ Method of drinking water
WO2013014373A1 (en) 2011-07-22 2013-01-31 Roquette Freres Potabilisation method
US20140197112A1 (en) * 2011-07-22 2014-07-17 Roquette Freres Potabilisation method
LT5926B (en) 2012-06-13 2013-04-25 Kauno technologijos universitetas Cationic starch flocculant and the method of production thereof
US9587353B2 (en) 2012-06-15 2017-03-07 Nanopaper, Llc Additives for papermaking
US9919938B2 (en) 2012-06-18 2018-03-20 Soane Mining, Llc Systems and methods for removing finely dispersed particles from mining wastewater
US10273169B2 (en) 2012-06-21 2019-04-30 Gavish-Galilee Bio Applications, Ltd. Method for pretreatment of wastewater with nanocomposites and bridging polymers
JP2016501121A (en) * 2012-11-16 2016-01-18 ロケット フレールRoquette Freres The process of drinking water
WO2014076435A1 (en) 2012-11-16 2014-05-22 Roquette Freres Potabilization process
CN104903252A (en) * 2013-04-18 2015-09-09 北京东方协和医药生物技术有限公司 A composition for treating waste water
WO2014171812A3 (en) * 2013-04-18 2015-05-07 ZAINAL ABIDIN, Roslan Bin A composition for treating waste water
CN104903252B (en) * 2013-04-18 2016-08-17 毛旭 For processing the compositions of waste water
WO2015073919A1 (en) * 2013-11-14 2015-05-21 University Medical Pharmaceuticals Corporation Microneedles for therapeutic agent delivery with improved mechanical properties
CN106414349A (en) * 2014-02-07 2017-02-15 罗盖特公司 Process for thickening or dehydrating sludge
FR3017384A1 (en) * 2014-02-07 2015-08-14 Roquette Freres PROCESS FOR THERAPY OR DEHYDRATION OF SLUDGE
WO2015118275A1 (en) * 2014-02-07 2015-08-13 Roquette Freres Process for thickening or dehydrating sludge
US10577259B2 (en) 2014-03-07 2020-03-03 Secure Natural Resources Llc Removal of arsenic from aqueous streams with cerium (IV) oxide compositions
US9975787B2 (en) 2014-03-07 2018-05-22 Secure Natural Resources Llc Removal of arsenic from aqueous streams with cerium (IV) oxide compositions
CN104876315A (en) * 2015-05-29 2015-09-02 鞍山中科美清节能环保技术有限公司 Water treatment flocculant
CN105084441A (en) * 2015-09-16 2015-11-25 太仓市国峰纺织印染有限责任公司 Printing and dyeing sewage treatment agent
US11192808B2 (en) 2016-03-17 2021-12-07 Gavish-Galilee Bio Applications Ltd. Method for production of potable water
IL261789B1 (en) * 2016-03-17 2024-06-01 Gavish Galilee Bio Appl Ltd Method for production of potable water
US20190152813A1 (en) * 2016-03-17 2019-05-23 Gavish-Galilee Bio Applications, Ltd. Method for production of potable water
IL261789B2 (en) * 2016-03-17 2024-10-01 Gavish Galilee Bio Applications Ltd Method for production of potable water
WO2017158581A1 (en) * 2016-03-17 2017-09-21 Gavish-Galilee Bio Applications Ltd. Method for production of potable water
CN106348411A (en) * 2016-10-13 2017-01-25 王家财 Novel clean environment-friendly coagulant and production method thereof
CN107162143A (en) * 2017-07-01 2017-09-15 辽东学院 Dyeing waste water purifies flocculant and its dyeing waste water purification applications
US20230183116A1 (en) * 2017-07-14 2023-06-15 Aquom Sciences Llc Biopolymeric water treatment
US11964893B2 (en) * 2017-07-14 2024-04-23 Keith Ervin Biopolymeric water treatment
US11572297B2 (en) * 2017-07-14 2023-02-07 Aquom Sciences Llc Biopolymeric water treatment
CN108773890A (en) * 2018-06-12 2018-11-09 赵田田 A kind of purifying domestic sewage agent and the preparation method and application thereof
US11155479B2 (en) 2018-11-21 2021-10-26 Baker Hughes Holdings Llc Methods and compositions for removing contaminants from wastewater streams
CN109761394A (en) * 2019-01-28 2019-05-17 合肥信拓高分子技术有限公司 A kind of stirring-type sewage-treatment plant
CN110217871A (en) * 2019-05-17 2019-09-10 茂名市水务投资集团有限公司 A kind of highly effective coagulation algae-removing method of the raw water containing algae
US11912594B2 (en) 2020-06-16 2024-02-27 Baker Hughes Oilfield Operations Llc Carbon disulfide-modified amine additives for separation of oil from water
WO2021257606A1 (en) * 2020-06-16 2021-12-23 Baker Hughes Oilfield Operations Llc Carbon disulfide-modified amine additives for separation of oil from water
US20220089463A1 (en) * 2020-09-22 2022-03-24 Aquom Sciences Llc Biopolymeric water treatment
CN114956292A (en) * 2022-05-13 2022-08-30 吉林农业大学 Method for pretreating soybean yellow serofluid by using chitosan flocculation
CN114956292B (en) * 2022-05-13 2024-05-14 吉林农业大学 Method for pretreating soybean whey by using chitosan flocculation
CN115092998A (en) * 2022-07-04 2022-09-23 庆阳新庄煤业有限公司新庄煤矿 Salt-reducing ash-reducing coal dust-removing flocculating agent for return air main roadway water collecting tank
WO2024073798A1 (en) * 2022-10-03 2024-04-11 The University Of Sydney Composite coagulants

Similar Documents

Publication Publication Date Title
US5543056A (en) Method of drinking water treatment with natural cationic polymers
Katrivesis et al. Revisiting of coagulation-flocculation processes in the production of potable water
Bratby Coagulation and flocculation in water and wastewater treatment
US6120690A (en) Clarification of water and wastewater
Semerjian et al. High-pH–magnesium coagulation–flocculation in wastewater treatment
CN104903252B (en) For processing the compositions of waste water
US7384573B2 (en) Compositions for wastewater treatment
Ayeche Treatment by coagulation-flocculation of dairy wastewater with the residual lime of National Algerian Industrial Gases Company (NIGC-Annaba)
US20100150818A1 (en) Clarification of water and wastewater
US5667697A (en) Colloidal silica/polyelectrolyte blends for natural water clarification
US20020189998A1 (en) Processes and apparatus for potable water purification that include bio-filtration, and treated water from such processes and apparatus
Stuetz et al. Principles of water and wastewater treatment processes
Akinnawo et al. Chemical coagulation and biological techniques for wastewater treatment
Rusten et al. Coagulation as pretreatment of food industry wastewater
AU4810501A (en) Method for treating contaminated liquid
Sarma Filtration and chemical treatment of waterborne pathogens
JP2000246013A (en) Flocculating sedimentation agent and flocculation treatment method
KR100313187B1 (en) Rapid mixing coagulant system for treating wastewater and method thereof
CA1334543C (en) Method for the treatment of sewage and other impure water
WO2000009453A1 (en) Clarification of water and wastewater
Shabe et al. Coagulation-Flocculation process to treat Pulp and Paper Mill Wastewater by Fenugreek Mucilage Coupled with Alum and Polyaluminum Chloride
Ali et al. Application of synthetic and grafted polymeric flocculants in agricultural wastewater treatment
WO2002026638A1 (en) Improved system and processes for water purification that include bio-filtration
Mohammed Ammonia removal from surface water in water purification plants on Rosetta branch
Murcott et al. MIT jar tests of Wachusett Reservoir water using the natural polymer chitosan with bentonite

Legal Events

Date Code Title Description
AS Assignment

Owner name: MASSACHUSETTS INSTITUTE OF TECHNOLOGY, MASSACHUSET

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MURCOTT, SUSAN E.;HARLEMAN, DONALD R.F.;REEL/FRAME:007212/0678

Effective date: 19940921

AS Assignment

Owner name: U.S. DEPARTMENT OF COMMERCE, DISTRICT OF COLUMBIA

Free format text: CONFIRMATORY LICENSE;ASSIGNOR:MASSACHUSSETS INSTITUTE OF TECHNOLOGY;REEL/FRAME:008370/0139

Effective date: 19950328

FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: SMALL ENTITY

FPAY Fee payment

Year of fee payment: 4

SULP Surcharge for late payment
REMI Maintenance fee reminder mailed
LAPS Lapse for failure to pay maintenance fees
FP Lapsed due to failure to pay maintenance fee

Effective date: 20040806

STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362